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MM209 - Thermodynamics

Instructor : Aswani Yella


Introduction
Thermo – Heat
Thermodynamics
Dynamics - Force

Understanding of thermodynamics centered around the concept of


getting power from hot bodies or getting power from heat

Thermodynamics is encountered in our daily life

There are several physical processes that occur in nature.

Some are spontaneous processes that occur in nature and some are non-
spontaneous in nature but we cause them to occur

There is always a rhythm for all physical processes in nature to occur


Introduction

All natural processes in nature have got a rhythm

They occur with certain directional constraints

For an example, the spontaneous processes that a water falls from


higher elevation to lower elevation

Heat flows from high temperature to low temperature not the reverse
way but there are many processes which we cause to occur, they also do
not occur in the reverse way naturally

For example, the conversion of mechanical energy into heat or


intermolecular energy is possible.
Introduction
•  Thermodynamics is that branch of science which deals with the
study of the transfer and conversion of energy from one form into
other and its conversion to work.
•  It deals with only conventional forms of energies like electrical,
mechanical, chemical. etc.
•  The non-conventional energy like nuclear energy related to atomic
and sub-atomic particle forms has to be dealt separately because in
that case all matter would have to be considered as per the famous
Einstein s equation :
E = mC2 .
Introduction

•  Here the subject matter of discussion is chemical and/or


metallurgical thermodynamics alone.
•  The systems under discussions consisting of large no. of
particles i.e., macro systems.
Classification
Thermodynamics may be broadly classified into three :
•  Classical: it treats a substance as continuum, ignoring behavior
of atoms and molecules. It consists of first, second and third
laws of thermodynamics
Introduction

•  Statistical thermodynamics: The application of probability


theory, quantum theory and statistical mechanics allowed it to
arrive at macroscopic thermodynamic relations from atomistic
point of view.

•  Irreversible Thermodynamics: Irreversible thermodynamics


deals with the application of thermodynamics to irreversible
processes such as chemical reactions.

The thermodynamics generally means classical


thermodynamics
Introduction

Energy
It is the ability to do work. This is too mechanical an answer.
The broader definition is : it is the capacity to bring about changes in the
existing materials as per the requirements.
Forms of energies
•  Mechanical: Kinetic, potential and configurational.
•  Thermal: Heat exchanged.
•  Electrical: Electrical energy = current x time x potential difference.
•  Chemical: Chemical energy = no. of chemical bonds x bond strength
Introduction

Key step in engineering analysis is to describe precisely what is being


studied

Eg: In Mechanics, If motion of body is to be determined

First step to define a free body, then identify all forces exerted on it

Then apply Newton's second law of motion


Introduction

THERMODYNAMICS à The term ‘System’ is used to identify the


subject of analysis.

Once the system is defined and relevant interactions with other systems
are identified.

Then one or more physical laws can be applied.


Introduction

Ø  In our study of thermodynamics, we will choose a small part of the


universe to which we will apply the laws of thermodynamics. We
call this subset a SYSTEM.

Ø  The thermodynamic system is analogous to the free body diagram


to which we apply the laws of mechanics, (i.e. Newton’s Laws of
Motion).

Ø  The system is a macroscopically identifiable collection of matter on


which we focus our attention (eg: the water kettle or the aircraft
engine).
Introduction

•  Any portion of the universe selected for consideration is known as the


system or thermodynamic system.

•  A thermodynamic system must, of necessity be stable with respect to


its chemistry during its study. If the system is undergoing
continuously some chemical change cannot be considered as system

•  For example a live animate body like tree and human being are not
system. All inanimate aggregates are called systems as they have their
fixed chemistry
Introduction

Ø  The rest of the universe outside the system close enough to the
system to have some perceptible effect on the system is called the
surroundings.
Important  note:  in  engineering  all  equations  must  be  dimensionally  homogenous.  This 
means that every term in an equation must have the same units. It can be used as a sanity 
check for your solution. 
Example 1: Unit Conversion 
The heat dissipation rate density of an electronic device is reported as 10.72 mW/mm2 by 
Ø  The surfaces which separates the system from the surroundings are
the manufacturer. Convert this to W/m2. 

called the boundaries10.as 72 shown in fig below


10720 (eg: walls of the kettle,
2
mW 1000mm 1W W
2
  2
mm 1m 1000mW m
the housingClosed and Open Systems 
of the engine).
A  system  is  defined  as  a  quantity  of  matter  or  a  region  in  space  chosen  for  study.    The 
mass or region outside the system is called the surroundings.  
 
 
BOUNDARY 
  SURROUNDINGS 
  SYSTEM 

 
 
 
Fig. 1: System, surroundings, and boundary 
check for your solution. 
Example 1: Unit Conversion 

Introduction
The heat dissipation rate density of an electronic device is reported as 10.72 mW/mm2 by 
the manufacturer. Convert this to W/m2. 
2
mW 1000mm 1W W
10.72 10720  
mm 2 1m 1000mW m2

Two types of exchange can occur between the system and its
Closed and Open Systems 

surroundings:
A  system  is  defined  as  a  quantity  of  matter  or  a  region  in  space  chosen  for  study.    The 
mass or region outside the system is called the surroundings.  
 
 
BOUNDARY 
  SURROUNDINGS 
  SYSTEM 

  Energy
 
 
Fig. 1: System, surroundings, and boundary 

1.  Energy
 
exchange (heat or work)
Boundary: the real or imaginary surface that separates the system from its surroundings. 
2.  Exchange of matter (movement of molecules across the boundary of
The boundaries of a system can be fixed or movable. Mathematically, the boundary has 
zero thickness, no mass, and no volume. 
theClosed system or control mass: consists of a fixed amount of mass, and no mass can cross 
system and surroundings).
its boundary. But, energy in the form of heat  or work, can  cross the boundary, and the 
volume of a closed system does not have to be fixed. 
Open system or control volume: is a properly selected region in space. It usually encloses 
a device that involves mass flow such as a compressor. Both mass and energy can cross 
the boundary of a control volume. 
Important note: some thermodynamics relations that are applicable to closed and open 
systems are different. Thus, it is extremely important to recognize the type of system we 
have before start analyzing it. 
Introduction

Types of Systems Types of System


Based on the types of exchange, one can define three different types of
systems

Closed system - in which Closed system


no mass is -permitted
in whichtono masstheis system
cross permitted to cros
boundary i.e. we would system
always boundary
consider i.e. we would
a system alwaysmass.
of constant consider a sy
do permit heat and ofwork
constant
:  A  closed  or  open  system  that  does  not  exchange 
We to mass.We
energy  with 
enter the 
or dobut
leave permit
not heat and work to ent
mass.
eat. 
leave but not mass.
Boundary Heat/work
Out
mass 
system
CLOSED 
SYSTEM  Heat/work
m = const. in
energy 
No mass entry or exit
Introduction
mass 

Open system-
CLOSED  in which weOpenpermitsystem-
mass toincross the system
which boundary
we permit mass in
to cross
either direction
SYSTEM  (from the system to surroundings
boundary in either or vice(from
direction versa). Insystem to su
the
analysing open systems, weortypically
m = const.
vice lookInatanalysing
versa). a specifiedopen
region of space,
systems, we typic
energy 
and observe what happens aatspecified
the boundaries
regionofofthat region.
space, and observe what hap
boundaries of that region.
Most of the engineering devices are open system.
osed system, mass cannot cross the boundaries, but energy can. 

Most of the engineering devices are open system.


mass 
Boundary
Heat/work Mass
Out out
CONTROL   System
VOLUME 
Heat/work
energy Mass in
In
 
ontrol volume, both mass and energy can cross the boundaries. 
c The Internet is predominately used for consumer and business commerce.

Power generation
c Electricity plays a greater role throughout society.

Introduction
c Wind, solar, and other renewable technologies contribute a significant share of the nation's
electricity needs.
c A mix of conventional fossil-fueled and nuclear power plants provides a smaller, but still
significant, share of the nation's electricity needs.
c A smart and secure national power transmission grid is in place.

A special type of closed system that Closed


does not interact in any way with its surroundings is called
1.2.1 Systems
an isolated system
closed system A closed system is defined when a particular quantity of matter is under study. A
closed system always contains the same matter. There can be no transfer of mass
across its boundary. A special type of closed system that does not interact in any way
isolated system with its surroundings is called an isolated system.
When the valves are closed, we can consider
Figure 1.1 shows a gas in a piston–cylinder assembly. When the valves are closed,
the gas to be a closed system
we can consider the gas to be a closed system. The boundary lies just inside the pis-
ton and cylinder walls, as shown by the dashed lines on the figure. Since the portion
of the boundary between the gas and the piston moves with the piston, the system
Gas Boundary
volume varies. No mass would cross this or any other part of the boundary. If com-
bustion occurs, the composition of the system changes as the initial combustible mix-
ture becomes products of combustion.

1.2.2 Control
The Volumes
boundary lies just inside the piston and
cylinder walls
In subsequent sections of this book, we perform thermodynamic analyses of devices
such as turbines and pumps through which mass flows. These analyses can be con-
ducted in principle by studying a particular quantity of matter, a closed system, as it
passes through the device. In most cases it is simpler to think instead in terms of a
given region of space through which mass flows. With this approach, a region within
Fig. 1.1 Closed system: A gas a prescribed boundary is studied. The region is called a control volume. Mass crosses
Closed system: A gas in a piston–cylinder assembly.
in a piston–cylinder assembly. the boundary of a control volume.
A diagram of an engine is shown in Fig. 1.2a. The dashed line defines a control
control volume volume that surrounds the engine. Observe that air, fuel, and exhaust gases cross the
boundary. A schematic such as in Fig. 1.2b often suffices for engineering analysis.
Introduction
The system boundary should be delineated carefully before proceeding with any thermodynamic
Chapter 1 Getting Started
analysis
Air
KE NOTE...
mations reinforce many
he text presentations.
can view these anima-
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ext content while In general, the choice of system boundary is governed by two considerations:
Tabs a, b, & c refers to (1) what is known about a possible system, particularly at its boundaries, and (2) the
The same physical phenomena often can be analyzed in terms of alternative choices of the
articular animation
and the tabs (Tabs a,
objective of the analysis.

system, boundary, and surroundings.


) of the animation
mended for viewing Figure 1.5 shows a sketch of an air compressor connected to a
o enhance your
storage tank. The system boundary shown on the figure encloses the compressor, tank,
standing.
and all of the piping. This boundary might be selected if the electrical power input
is known, and the objective of the analysis is to determine how long the compressor
The choice of a particular boundary defining a particular system depends heavily on the
must operate for the pressure in the tank to rise to a specified value. Since mass
convenience it allows in the subsequent analysis.
crosses the boundary, the system would be a control volume. A control volume
enclosing only the compressor might be chosen if the condition of the air entering
System_Types and exiting the compressor is known, and the objective is to determine the electric
A.1 – Tabs a, b, & c
power input. b b b b b

In general, the choice of system boundary is governed by two considerations: (1) what is known
about a possible system, Systems
1.3 Describing particularly
andatTheir
its boundaries,
Behavior and (2) the objective of the analysis.
Engineers are interested in studying systems and how they interact with their sur-
roundings. In this section, we introduce several terms and concepts used to describe
systems and how they behave.
pter 1 Getting Started

OTE...
Introduction Air

ns reinforce many
xt presentations.
ew these anima-
oing to the
ompanion site
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ook. Air compressor
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ntent by an icon
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ontent while In general, the choice of system boundary is governed by two considerations:
a, b, & c refers to (1) what is known about a possible system, particularly at its boundaries, and (2) the
lar animation
he tabs (Tabs a,
The system boundary shown on the figure encloses the compressor, tank, and all of the piping.
objective of the analysis.

he animation
ed for viewing Figure 1.5 shows a sketch of an air compressor connected to a
ance your storage tank. The system boundary shown on the figure encloses the compressor, tank,
ing. and all of the piping. This boundary might be selected if the electrical power input
This boundary might be selected if the electrical power input is known, and the objective of the
is known, and the objective of the analysis is to determine how long the compressor
analysis is to determine how long the compressor must operate for the pressure in the tank to rise
must operate for the pressure in the tank to rise to a specified value. Since mass
crosses the boundary, the system would be a control volume. A control volume
to a specified value
System_Types
enclosing only the compressor might be chosen if the condition of the air entering
and exiting the compressor is known, and the objective is to determine the electric
1 – Tabs a, b, & c
power input. b b b b b

Since1.3 Describing
mass crosses theSystems andthe
boundary, Their Behavior
system would be a control volume.
Engineers are interested in studying systems and how they interact with their sur-
roundings. In this section, we introduce several terms and concepts used to describe
systems and how they behave.

1.3.1 Macroscopic and Microscopic Views of Thermodynamics


Systems can be studied from a macroscopic or a microscopic point of view. The mac-
Introduction

er 1 Getting Started

Air
TE...
reinforce many
presentations.
these anima-
ng to the
mpanion site
Tank
. Air compressor
ns are keyed to
ent by an icon
.
of these icons Fig. 1.5 Air compressor and storage
ctly below. In tank. +

the label
es refers to
ent while In general, the choice of system boundary is governed by two considerations:
, & c refers to (1) what is known about a possible system, particularly at its boundaries, and (2) the
animation A control volume enclosing only the compressor might be chosen if the condition of the air
objective of the analysis.
entering and exiting the compressor is known, and the objective is to determine the electric
tabs (Tabs a,
animation
for viewing
ce your
power input Figure 1.5 shows a sketch of an air compressor connected to a
storage tank. The system boundary shown on the figure encloses the compressor, tank,
. and all of the piping. This boundary might be selected if the electrical power input
is known, and the objective of the analysis is to determine how long the compressor
must operate for the pressure in the tank to rise to a specified value. Since mass
crosses the boundary, the system would be a control volume. A control volume
enclosing only the compressor might be chosen if the condition of the air entering
ystem_Types and exiting the compressor is known, and the objective is to determine the electric
– Tabs a, b, & c
power input. b b b b b

1.3 Describing Systems and Their Behavior


Engineers are interested in studying systems and how they interact with their sur-
Introduction
•  At any given instant of observation the condition of the system is
described by an appropriate set of properties
•  Limitations on the changes in these properties are set by the nature of
the boundary
•  At the onset of the consideration of any problem classify the system
under study according to the following five categories
1. Closed vs open versus isolated
2. Unary vs multi-component
3. Homogeneous vs heterogeneous
4. Reacting vs non reacting
5. Otherwise simple vs complex
Introduction

Closed versus Open --- Is matter exchanged with the surroundings?

Unary versus Multicomponent --- How many unique chemical


species?

Homogeneous versus Heterogeneous --- How many unique


phases?

Non-reacting versus Reacting --- Can chemical reactions occur?

Otherwise Simple versus Complex --- Are only chemical, thermal,


or mechanical effects involved? Are fields, surfaces, or elastic
effects involved?
Introduction
•  Unary vs multi-component
Identifies the complexity of the chemistry of the system
Simplest chemical composition are unary à One chemical component
More than one chemical component à multi-component
•  Homogeneous vs heterogeneous
Specific thermodynamic meaning à single phase
Mix of water and ice à composed of more than one phase
•  Reacting vs non reacting
Systems that can exhibit chemical reactions.
•  Otherwise simple vs complex
•  Capable of energy exchange other than thermal, mechanical or chemical ch
i.e., gravitational, electrical, magnetic or surface influences then it is classi
complex category.
'surroundings'. The system may exchange matter or energy or both with the surroundings
during the change. The thermodynamic systens can be classified based on its interaction
Introduction
with the surroundings or on its orrun material distribution or on its o\,vn composition as shown
in Fig.1.1.

THEROMODYNAMIC SYSTEMS

IN TERMS OF ITS BASED ON


INTERACT]ONS MATERIAL COMPOSITION
THE SURROUNDINGS DISTRIBUTION

ISOLATED- OPEN BOTH CLOSED SINGLE MULTI-COMPONENT


gCHANG. MATTER AND CAN Q,A COMPONENT
ES NEITHER
MATTER
ENERGY
EXCI.IANGE
E(CHA.
NGE
Xu
Ei
fi O
H@
de
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NOR
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WITH THE
OCCURS EN E RGY
BUT NOT
MATTEB
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@
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ri
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o

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:)

U.r
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!=
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SURROUND
o *u) oX(E
INGS
o
5xg
irJv aoi!
= == J!I

Fig. 1.1 - Classification of tkermodynamic systems.

Atherrnodynamicsystemmust, of necessity, be stablewithrespecttoitschemistry


Introduction
We now introduce several terms and concepts used to describe systems
and how they behave.
Property
State
Process
To describe a system and predict its behavior requires knowledge of its
properties and how those properties are related.

A property is a macroscopic characteristic of a system such as mass,


volume, energy, pressure, and temperature to which a numerical value
can be assigned at a given time without knowledge of the previous
behavior (history) of the system.
Introduction
State

The word “State” refers to the condition of a system as described by its


properties

Since there are normally relations among the properties of a system, the
state often can be specified by providing the values of a subset of the
properties

Subset of Universe that is in System Surroundings


focus (SYSTEM)
T, P, XK, V
Boundary
State
•  Condition of the system as described by its properties.
•  Usually only a subset of properties need to be specified
to identify the state of a system.
•  Some difficulties in specifying “state” of a system.
–  State of the world
–  State of the “hot potato”

The idea of equilibrium comes to rescue.


Introduction

•  As the position of a point in the space is described by its coordinates w.r.t


some prefixed axes, similarly the state of a system is described by some
experimentally determinable parameter which can lead to the complete
reproduction of the system.

•  These parameters are temperature, pressure and volume.

•  The minimum number of variable required to describe the state of the system
are called independent state variables.
Introduction

•  Incase of a multicomponent system the independent state variables are i)


composition ii) two of the three variables T, P, V.

•  All other variables whose values get fixed with the specification of
independent state variables are referred to as dependent state variables.

•  State variables are also known as state properties or state functions.


Introduction

Two types of state properties

Intensive Extensive

•  If a state variable, whether dependent or independent, is a function of the mass


of the system it is known as extensive state property. For example: Mass,
Volume, weight, length, energy etc.

•  If a state variable is independent of the mass or size of the system it is called


intensive state property. For example: temperature, pressure, conductivity,
density, colour, odor, malleabilty, hardness, specific heat, molar volume etc.
Intensive and Extensive Properties

There are certain properties which depend on the size or extent of the system, and there are certain

Introduction
properties which are independent of the size or extent of the system. The properties like volume,
which depend on the size of the system are called extensive properties. The properties, like
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 exact replica of itself to create a new system differing only by size.
Assume two identical systems S and S as shown in Figure . Both the
Intensive properties are those which are unchanged by this process, whereas those properties
whose values are increased or decreased 1 in proportion to2 the enlargement or reduction of the
systems are in identical states.
system are called extensive properties.

Assume two identical systems S and S as shown in Figure 2.1 . Both the systems are in identical
1 2
Let S3 be the combined system.
states.
Let S be the combined system. Is the value of property for S same as that for S (and S )?
3 3 1 2

Figure 2.1
Is the value Ifof property for S3 issame
the answer is yes, then the property intensive
as that for S1 (and S2 )?
If the answer is no, then the property is extensive

IfThethe answer is yes, then the property is intensive


ratio of the extensive property to the mass is called the specific value of that property

specific volume, v = V/m = 1/ ρ ( ρ is the density)


Ifspecific
theinternal
answer is no, then the property is extensive
energy, u = U/m

Similarly, the molar properties are defined as the ratios of the properties to the mole number (N) of
the substance
Introduction
•  Comparison of two systems :
Both have identical intensive properties
Double the quantity of matter à double the extensive properties

•  Extensive propertiesà can change with time


Many thermodynamic analysis consists mainly of carefully accounting for
changes in extensive properties as system interacts with surroundings.

•  Intensive propertiesà Defined to have a value at a point in the system.


Are not additive in the sense previously considered
Values independent of the size of the system and many vary from place to
place within the system at any moment

•  Intensive properties àfunction of position and time


•  Extensive properties àfunction of time
Intensive properties: are those that are independent of the size (mass) of a system, such 
Introduction
as temperature, pressure, and density. They are not additive. 
Extensive  properties:  values  that  are  dependant  on  size  of  the  system  such  as  mass, 
volume, and total energy U. They are additive. 
Example:- Temperature, pressure, density, boiling point,etc
canGenerally, uppercase letters are used to denote extensive properties (except mass 
have a different value at different points
m),  and  lower  case  letters  are  used  for  intensive  properties  (except  pressure  P, 
temperature T).  
Pressure varies
Extensive  withper height
properties  as well
unit  mass  as horizontally.
are  called  specific  properties,  e.g.  specific 
volume (v=V/m). 

extensive  
m  properties  0.5m  0.5m 
V  0.5V  0.5V 
T     
P  T  T 
  P  P 
intensive  
properties 

 
Fig. 1‐5: Intensive and extensive properties of a system. 
Introduction
•  Example:- Temperature, pressure, density, boiling point

can have a different value at different points


Pressure varies with height as well as horizontally.

It is possible to derive an intensive property for each of the extensive


properties defined in thermodynamics

Such a definition visualizes a limit of the ratio of two extensive


properties in a small region of the system

Example :- Molar concentration of a component (K)


ratio of small volume element neighbouring the point (∆V) and the
number of moles of component (∆nK )
Introduction
Extensive properties are not just dependent on the amount of material
in a system

The relation must be additive.

Eg: Let's say a property depended on the square of the mass.

A system consisting of two 1 g mass


Total mass à 2 g
Squaring total mass à 4g2
Squaring and summing individual masses à 2g2

Property not additive to subsystems à So not an extensive property


Introduction

The ratio of the extensive property to the mass is called the specific
value of that property

specific volume, v = V/m = 1/ ρ ( ρ is the density)

specific internal energy, u = U/m

The molar properties are defined as the ratios of the properties to the
mole number (N) of the substance

Molar volume = = V/N

Molar internal energy = = U/N


Introduction

•  Product of an intensive and an extensive state variable is also an


extensive state variable.

•  Ratio of two extensive properties yields an intensive properties.


For example: Density = m / V

•  The general convention in thermodynamics is to go for molar


properties, which are intensive and become independent of
quantity of matter and hence of more general applicability.
Introduction

At a given state, each property has a definite value that can be assigned
without knowledge of how the system arrived at that state.

The change in value of a property as the system is altered from one


state to another is determined, therefore, solely by the two end states
and is independent of the particular way the change of state occurred

Thermodynamics also deals with quantities that are not properties, such
as mass flow rates and energy transfers by work and heat.
Introduction

•  A material system may under go a change, under


externally or internally imposed constraints, in
terms of their state variables from the existing one
to some different values.

•  For example: Expansion of a gas from V1 to V2


may be called as a thermodynamic process.
Introduction

Process

When any of the properties of a system changes, the state changes and
the system is said to undergo a process

A process is a transformation from one state to another.

Process System
System

T1, P1, X1, V1


T, P, X, V
Introduction
Many a times such processes are carried out under additionally imposed conditions and are
named accordingly. Such processes are:

•  Isothermal processes: These are the processes which proceed


without any change in temperature of the system e. g. melting of
ice or metal. dT = 0

•  Isobaric process: These are the processes which proceed without


any change in pressure of the system e.g. processes carried out in
open atmosphere. dP = 0

•  Isochoric Processes: These are the processes which proceed


without any change in volume of the system e.g. the processes
carried out in vessel of known volume . dV = 0
ryray
or it
Introduction
nray not be known.
There can be sereral such relationships correlating the available state propedies
of a particular system and all such relationships shali be called as equations of state for
that particular system. These are useful relationships to calculate the required
state
properties' knowing sone others.
•  Adiabatic processes: These are the processes which proceed
1.7 THEREMODYNAMIC PROCESS

without any exchange of heat by the system with its


A material undergo a change,
system may externally under or internally irnposed

constraints, terms of their state variables, from the existing one


in to sorne different

variables. such a'thermodynamic process''


a change in the state of the system is known as
surrounding e.it g. two
the system into is pieces
pieces. But if the
into
completely
lf a ten meter long rod is cut
of
in
two
process
insulated
the energy
breaking, to
of
from the
the change is merely a physical one
the rod
required break
breaking
is
of breakingγ to be a thernnodynamic
surrounding . dq = similarly
0. for if ironideal gas PVto form=itsconst.
oxide, it is aγ = Cp/Cv
taken into the
consideration then process is considered
withcombines oxygen simple chemical
process.
process but if the energy exchanged in this process is taken into account
then this process
process takes place
•  Polytropic Processes: Those processes which obey equation
of oxidation is a thermodynamic process' The way the thernndynamic
is known as its
,process path'. There are different types of thermodynamic processes
named accordingly and are
depending upon the conditions imposed on the system and are
PVn = const where n is any positive number between 1 and γ.
shown in Fig. 1.2.

lsoBARlc
Fis.12 -
Sc he matic tion of
re Pre s e nta

g pressure vs. volurrte in vqri-


tr G
E ous
f o tkermodYnamic Proc-
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rt (, €.ss'es like isabaric,
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o. kolhermal, isochoric, adi-
abatic and polytroPic-

VOLIJME
Introduction
If a system exhibits the same values of its properties at two different
times, it is in the same state at these times

A system is said to be at steady state if none of its properties changes


with time.

Two different kinds of properties

State Process
Does not depend on how Depends on the path
the system arrived at that followed to come to that
condition condition
Introduction
•  The property whose change depends on only the initial and
final states of the system not on the path adopted to bring
about the change is called state function.
•  Mathematically if the property is a state function (X) then in
a cyclic process, when system under goes a change and
returns to original state then
Ф dX = 0
•  If Y is not a state function
Ф δY ≠ 0
So Y is called a path function
Introduction

Mere algebric summation of the values of the state functions gives the
change in the state

But in case of assessing the work and heat exchange effects such a
summation does not lead to the required value as these are not state
functions.

Whether any function is a state function or not can be mathematically


assessed
time without knowledge Theof the pastofhistory
value aand of the
property of system.
a systemMany other properties
is independent of the are considered
during the course
volume, of
energy, our study.
pressure temperature to which numerical values canprocess or theatpaa
be assigned
during the course of our study.
system in reaching a particular state.
time without knowledge of the past history of the system. Many other properties are cons
Theofvalue
The value Introduction
during the course of our study.
of a
a property
The property
of a system
change ofisvalue
in the aindependent
system
of theisproperty
independent
of the process
dependsofonly
or thepath
the process
on followed
the or and
initial thethe
by path
the f
system system in
in reaching reaching
a particulara particular
state. state.
The value of a property of a system is independent of the process or the path followed
Thesystem
word in reaching
state refers a particular state.
to the condition of a system as described by its proper
The change in the value of the property depends only on the initial andonthethefinal states.
Mathematically, if P is a property of the system, then the change in the
The change in the value of the property depends
The change in ifthe
only initial and the fin
Mathematically, P value of the property
is a property of thedepends
system,only
thenon the
the initial
change andinthe final
the states.
property
property in going from the initial state 1 to the final state 2 is given by
The word state refers
The wordinitial
to the1condition
statestate
referstoto finalof
thethe a system
state
condition
as described
2 is given by
of a system
by its properties.
as described by its propertie
The word state refers to the condition of a system as described by its properties.
Mathematically, if P is a property of the system, then the change in the property in going from the
Mathematically,
initial state if P 2ifisis
1 toMathematically,
the final state Pagiven
isproperty
a property
by ofof the system,then
the system, then
the the change
change in the in the property
property in going frin
initial state
initial1state
to the
1 tofinal state
the final 2 2isisgiven
state by
given by

•  If a system has two independent variables say x and y and any other
If P = P (x, y) then,
function or property can be expressed in its total differential form
If P = P (x, y) then,
If P = P (x, y) then,
P
If P = P (x, y) then, = P (x, y)
where,

where, where,

where,

If , then dP is said to be an exact differential, and P is a

If,If If
, then dP
dP is
is , said
thentoto
said dP
be is
bean said
an to differential
exact
exactbedifferential,
an exact differential,
and P is and
a P isfunction.
point a point A
func
thermodynamic property is a point function and not a path function. Pressure, tem
or molar volume
thermodynamic propertyareissome of function
a point the quantities
and notwhich
a path satisfy these
function. requirements.
Pressure, temperature, v
thermodynamic property is a point function and not a path function. Pressure, temperature, volume
Properties of State Function
The function P is a state variable if and only if it is
an exact differential
⎛ ∂a ⎞ ⎛ ∂b ⎞
⎜ ⎟ =⎜ ⎟
⎝ ∂y ⎠ X ⎝ ∂x ⎠Y

Consider the volume, V, of 1 mole of a pure gas

The value of the volume is dependent on the values of the pressure, P,


and temperature, T, of the gas

V =V(P,T)

Fixing the values of any two of the three variables fixes the value of
the third variable of the system when it is in equilibrium
b P2
T
T1 T2 Introduction
P P1
In a three-dimensionalP2diagram, the coordinates of which are volume,
pressure,
quilibrium and
states of temperature,
existence theofpoints
for 1 mole gas inin V-P-T
V -P space
-T space, which
shown represent the
to lie
T1 T2
urface.equilibrium
P states of existence
6 of the system lieTOon
INTRODUCTION THEaTHERMODYNAMICS
surface OF MATERIALS,

V
quilibrium states of
Consider ∆V = Vwhich
a existence
process − 1V1mole
2for of gasthe
changes in Vstate
-P -T space,
of shown to lie
urface.
the gas from state 1 to state 2
ld proceed along many different paths on the V -P -T surface, two
→ 2 and 1 → b → 2, are shown in Figure 1.1. Consider the path a
∆V = V2 − V1 1
change in volume is
2
ld proceed along many different paths on the V -P -T surface, two
b

→ 2 and 1 →∆bV→ =∆ + ∆Va →in T


2,Vare
1 →a shown 2 Figure 1.1. Consider the path
change in volume is P1
∆V = (Va − V1 ) + (V2 − Va ) P2

∆V = ∆V1 →a + ∆Va →2 P
T1 T2

∆V = V2 − V1
∆V = (Va − V1 ) + (V2 − Figure
Va ) 1.1 The equilibrium states of existence for 1 mole of gas in V -P -T sp
on a surface.
at the constant temperature, T2 ∆V = V2 − V1
at the constant pressure, P1 Introduction
satthese
the constant
changestemperature,
where: as T2
1 → a occurs at the constant pressure, P1
→ 2 occurs
ss thesea changes as at the constant
T2 temperature, T2
⎛ ∂V6 ⎞
∆V1→a = V a − V1 = ⎜
T 2⎝ ∂
We can express these TchangesT∫ ⎟
⎠ as
dT
INTRODUCTION TO THE THERMODYNAMICS OF MATERIALS,

⎛ ∂V ⎞P1

1
V
∆V1→a = V a − V1 = ⎜ ⎟ dT
⎝ ∂ T ⎠ T2
T
⎛ ∂V ⎞

1 P1
∆V1→a = V a − V1 = ⎜ ∂T ⎟ dT
P2 ⎝ ⎠
⎛ ∂V ⎞

T1 P1 1 a
∆V a→2 =OF
ON AND DEFINITION
−Va = ⎜
V 2TERMS ⎟ dP 7
P⎝ ∂ P ⎠
and P1 2
2
⎛ ∂V ⎞T 2 b
∆V a→2 = V 2 − V a = ⎜
⎝ ∫
∂P ⎠ ⎟ dP
P2
⎛ ∂V ⎞
T


P1 P1
T2
T2 ∆V
P2 a → 2 = V 2 − V a = ⎜ ∂P ⎟ dP P2
⎛ ∂V ⎞ ⎛ ∂V ⎞ ⎝ ⎠ T
∆V =
1→2
∫ ⎜⎝ ∂T ⎟⎠
T1
dT +
P1
∫ ⎜⎝ ∂P ⎟⎠
P1
dP P

T2
T
P
1 1 T2 (1.2)
2

Figure 1.1 The equilibrium states of existence for 1 mole of gas in V -P -T sp


on a surface.
⎛ ∂V ⎞ ⎛ ∂V ⎞ ⎛ ∂V ⎞ ⎛ ∂V ⎞
e path 1 → b∆V→1→2:
∆V 1→2 =
T2 ⎝ ∫
⎜ ∂T ⎟

⎛T1∂V ⎞ P1
dT ∆V
+
P 2
⎜1→
⎝ ∂P ∫
2 ⎟=

P⎛1 ∂V ⎞ T 2 ⎝
dP
⎜ ∂T ∫ ⎠ ⎝ ∫
⎟ dT + ⎜ ∂(1.2)
P⎠⎟ dP
2 = ⎜ ∂T ⎟ dTIntroduction
∫ + ⎜
∫ ⎟ dP
T1 P1 P 1 (1.2) T2
T1
⎝ ⎠ P
⎝ ∂P ⎠
P1 T2
y, for the path 1 → b → 2:
1
P2
∂V→⎞ b → 2:
⎛1
Similarly, for the path
∆V 1→b = V b − V 1 = ⎜
or the path 1 → b → 2: ⎟ dP
⎝ ∫
∂P2P⎛ ∂⎠V ⎞
P2 ⎝ ∂P ⎠ ∫
∆V 1→b = V b − VP11 = ⎜ 6 T1 ⎟ dPINTRODUCTION TO THE P 2
THERMODYNAMICS OF MATERIALS,

⎛ ∂V ⎞

⎛1 ∂V ⎞ T1

P
∆V 1→b = V b − V 1 = ⎜ ∆V
⎟ 1→b = V b − V 1 =
dP ⎜
V ⎟ dP
P
⎝ ∂P ⎠
1 T1
⎝ ∂P ⎠ P1 T1
T2
⎛ ∂T 2V ⎞
and
∆V b→2 = V 2 − V b = ⎜
∫ ∫
⎛ ⎟
∂V
dT

∆V b→2 = V 2 − VTb ⎝= ∂P⎜ ⎠ ⎟ dT a
⎝ ∂P ⎠
1 T2 P2 1
⎛ ∂V ⎞
∫ ⎜⎝ ∂P ⎟⎠
T1 P2
∆V b→2 = V 2 − V b = dT T2 2
⎛ ∂V ⎞

b

P2
T1
T2
∆V b→2 = V 2 − V b =
P2
⎜ ∂P ⎟ dT T

⎛ ∂V ⎛⎞ ∂V ⎞ ⎛ T∂2V⎛ ∂⎞V ⎞ ⎝ ⎠
∫ ∫ ∫ ∫
P2
∆V 1→2∆V
= ⎜ = ⎟ dP +dP +⎜ ⎟ dTdT T1 P 2 P1
(1.3)
1→2 ∂P ⎜
⎝ P2 ⎝⎠ ∂P ⎟⎠ T⎝2 ∂T
⎜ ∂⎠T ⎟ (1.3) P2
⎝ ⎠
P1
⎛ ∂V ⎞ ⎛ ∂V ⎞ T1

∫ ∫
P1 T1 T1 P2 P2
Hence,
∆V 1→2 = ⎜ ⎟ dP + ⎜
T1
⎟ dT T1 T2
(1.3)
⎝ ∂P ⎠ ⎝ ∂T ⎠ P
P1 T1 T1 P 2 P2 T2
nd 1.3 must yield the same value of
s 1.2 and 1.3 must yield the same value ∆ V 21→.⎛2In
of ∆ V
Figure 1.11→The
.∂Vthe
In ⎞ limit
the limit of ⎛infini-
of infini-
∂V ⎞for 1 mole of gas in V-P-T sp
change in volume,
in volume, thesethese equations
equations ∆V
yieldyield = complete
2 the
the
1→
equilibrium
⎜a surface.
oncomplete dP + ⎜ of
states of existence
⎟ differential
differential of⎟ dT
P2 ∆VT = V2 − V1
2
⎛ ∂V ⎞ ⎛ ∂V ⎞
∫ ∆V 1→2
∫ = ⎜
P1


∂P ⎠
dP + ⎜
Introduction
T1 T


∂T ⎠
process could proceed along many different paths on the
1
dT
(1
P2

hich, 1 → a → 2 and 1 → b → 2, are shown in Figure 1.1


uations 1.2 and 1.3 must yield the same value of ∆ V 1→ 2 . In the limit of infi
→ In
aimal 2. The
the change
limit of in volume
infinitesimal change
change in volume, these equations
is
in volume,
yieldthese
the equations
completeyield the
differential
uationcomplete
1.1: differential

⎛ ∂V ∆
⎞V = ∆ ⎞ a + ∆Va →2
⎛ ∂VV1 →
dV = ⎜ ⎟ dP + ⎜ ⎟ dT (1
⎝ ∂P ⎠T ⎝ ∂T ⎠ P
∆V = (Va − V1 ) + (V2 − Va )
e change in volume caused by changing the state of the gas from state 1 to stat
pends The
onlychange
on the in volumeatcaused
volumes statesby changing
1 and 2 andthe state of the gas
is independent of from statetaken
the path
1 to statethe
gas between 2 depends only on
states. This is because ∆V
the volumes =states
the at V2 −1ofV
volume and
the2 and is
1 gas is a state functi
independent of the path taken by the gas between the states. This is
d Equation 1.4 is an exact differential of the volume, which is a thermodynam
because the volume of the gas is a state function
te variable.
e:The partial differentials which relate the change in volume to changes in t
→ a occurs
ensive at the constant
thermodynamic variables (Ppressure,
and T ) are Prelated
1 to the properties of t
→— namely,
2 occurs at the constant temperature, T
Relationship among state variables
Let there be three state functions X, Y and Z and two of these as
independent state variables. Once Z and once Y as dependent
variables. Thus
Z = Z (X, Y)
Y = Y (X, Z)
Total differential can be written as

⎛ ∂Z⎞ ⎛ ∂Z⎞
dZ = ⎜⎜ ⎟⎟ dX + ⎜⎜ ⎟⎟ dY
And ⎝ ∂ X ⎠Y ⎝ ∂ Y ⎠X
⎛∂Y⎞ ⎛∂Y⎞
dY = ⎜⎜ ⎟⎟ dX + ⎜⎜ ⎟⎟ dZ
⎝ ∂ X ⎠Z ⎝ ∂ Z ⎠X
Relationship among
state variables
Putting the value of dY in first expression leads to
⎡⎛ ∂ Z ⎞ ⎛ ∂Z ⎞ ⎛∂Y⎞ ⎤ ⎡ ⎛ ∂Z ⎞ ⎛∂Y⎞ ⎤
dZ = ⎢⎜⎜ ⎟⎟ + ⎜⎜ ⎟⎟ ⎜⎜ ⎟⎟ ⎥ dX + ⎢ ⎜⎜ ⎟⎟ ⎜⎜ ⎟⎟ dZ ⎥
⎢⎣⎝ ∂ X ⎠ Y ⎝ ∂ Y ⎠ X ⎝ ∂ X ⎠ Z ⎥⎦ ⎢⎣ ⎝ ∂ Y ⎠ X ⎝ ∂ Z ⎠ X ⎥⎦

equating the coefficients of dX and dZ on both


Sides, we get
⎛ ∂Z ⎞ ⎛∂Y⎞ ⎛ ∂Z⎞ 1
⎜⎜ ⎟⎟ ⎜⎜ ⎟⎟ = 1 ⇒ ⎜⎜ ⎟⎟ =
⎝ ∂ Y ⎠X ⎝ ∂ Z ⎠X ⎝ ∂ Y ⎠ X ⎛⎜ ∂ Y ⎞⎟
⎜ ∂Z⎟
⎝ ⎠X
⎛ ∂Z⎞ ⎛ ∂Z ⎞ ⎛∂Y⎞ ⎛ ∂Z⎞ ⎛ ∂Z ⎞ ⎛∂Y⎞
and ⎜
⎜ ⎟
⎟ ⎜
+⎜ ⎟
⎟ ⎜
⎜ ⎟
⎟ =0 ⇒ ⎜
⎜ ⎟
⎟ = − ⎜⎜ ⎟⎟ ⎜⎜ ⎟⎟
⎝ ∂ X ⎠Y ⎝ ∂ Y ⎠X ⎝ ∂ X ⎠Z ⎝ ∂ X ⎠Y ⎝ ∂ Y ⎠X ⎝ ∂ X ⎠Z
Relationship among
state variables
Similarly, ⎛∂Y⎞ 1 ⎛ ∂Z⎞ 1
⎜⎜ ⎟⎟ = ⎜⎜ ⎟⎟ =
⎝ ∂ X ⎠ Z ⎛⎜ ∂ X ⎞⎟ and ⎝ ∂ X ⎠ Y ⎛⎜ ∂ X ⎞⎟
⎜∂Y⎟ ⎜ ∂Z⎟
⎝ ⎠Z ⎝ ⎠Y
Finally after substitution we can write
⎛ ∂Z⎞ ⎛∂Y⎞ ⎛∂X⎞
⎜⎜ ⎟⎟ ⎜⎜ ⎟⎟ ⎜⎜ ⎟⎟ = − 1
⎝ ∂ Y ⎠X ⎝ ∂ X ⎠Z ⎝ ∂ Z ⎠Y
similarly
⎛∂X⎞ ⎛∂Y⎞ ⎛ ∂Z ⎞
⎜⎜ ⎟⎟ ⎜⎜ ⎟⎟ ⎜⎜ ⎟⎟ = − 1
⎝ ∂ Y ⎠Z ⎝ ∂ Z ⎠X ⎝ ∂ X ⎠Y
The above two expressions correlate the partial differentials of three state
variables w.r.t one another and are popularly called reciprocity theorem.
Introduction

Without state functions thermodynamics would


be useless. Discuss this assertion.

If there no state functions (like T, P, V, composition)


then the behavior of all aspects of matter would depend
explicitly on the history of the system.
There would be no variables that, by themselves,
explicitly describe the current condition of any system.
Even the history experienced by the system could not be
described in terms of some sequence of its properties.
MM209 - Thermodynamics
Instructor : Aswani Yella
Introduction

Defined the Thermodynamic terms


•  System, boundary, surroundings
•  Different thermodynamic systems
•  Property, state, process
•  Intensive and extensive variables
•  State Postulate
•  State and process functions

The function P is a state variable if and only if it is an exact


differential
⎛ ∂a ⎞ ⎛ ∂b ⎞ ⎛ ∂ X ⎞ ⎛ ∂Y ⎞ ⎛ ∂ Z ⎞
⎜ ⎟ =⎜ ⎟ ⎜ ⎟ ⎜ ⎟ ⎜ ⎟ = −1
⎝ ∂y ⎠ X ⎝ ∂x ⎠Y ⎝ ∂Y ⎠Z ⎝ ∂ Z ⎠ X ⎝ ∂ X ⎠Y
Introduction

Without state functions thermodynamics would


be useless. Discuss this assertion.

If there no state functions (like T, P, V, composition)


then the behavior of all aspects of matter would depend
explicitly on the history of the system.
There would be no variables that, by themselves,
explicitly describe the current condition of any system.
Even the history experienced by the system could not be
described in terms of some sequence of its properties.
Introduction
Driving forces and their conjugates:
All thermodynamic potentials are expressed in terms of conjugate pairs.
Many of the direct observables form conjugate pairs such that their
product has the dimensions of energy or sometimes power.

For a mechanical system, small increment of energy is the product of


force times small displacement.
Similar situation exists in thermodynamics.

An increment in the energy of a thermodynamic system can be


expressed as the sum of the products of certain “Generalized forces” that
when unbalanced causes certain “Generalized displacements”.

The product of the two is the energy transferred as a result.


Introduction

These forces and their associated displacement are called conjugate


variables.

Thermodynamic force à intensive variable always


Displacement à extensive variable
Yielding an extensive energy transfer
Introduction

These forces and their associated displacement are called conjugate


variables.
System Intensive variable Extensive
variable
Fluid Pressure P Volume V
Filament Tensional force F Length L
Film Surface Tension r Area A
Electrical Potential difference E Charge q
Dielectric Electric field E Dipole moment P
Magnetic Flux density B Dipole moment m
All system Temperature T Entropy S
Generalized Force F Displacement x
Introduction
Thermodynamic Equilibrium
•  When a system is placed in a new set of surroundings, it
usually be seen to undergo a change.
•  Bulb of thermometer -- beaker of warm water
•  Mercury expands and will rise in the capillary, after
sometime there is no further change (thermodynamic
Equilibrium)
Introduction
In mechanics, equilibrium means a condition of balance maintained by an equality of
opposing forces.

In thermodynamics, the concept is more far-reaching, including not only a balance of forces
but also a balance of other influences.

Each kind of influence refers to a particular aspect of thermodynamic, or complete equilibrium.

Several types of equilibrium must exist individually to fulfill the condition of complete
equilibrium; among these are mechanical, thermal, phase, and chemical equilibrium.

Test to see if a system is in thermodynamic equilibrium by the following procedure: Isolate the
system from its surroundings and watch for changes in its observable properties. If there are no
changes, we conclude that the system was in equilibrium at the moment it was isolated. The
system can be said to be at an equilibrium state.
Introduction
When a system is isolated, it does not interact with its surroundings; however, its state can
change as a consequence of spontaneous events occurring internally as its intensive properties,
such as temperature and pressure, tend toward uniform values

When all such changes cease, the system is in equilibrium

At equilibrium, temperature is uniform throughout the system. Also, pressure can be regarded as
uniform throughout as long as the effect of gravity is not significant

It is not necessary that a system undergoing a process be in equilibrium during the process.
Some or all of the intervening states may be non-equilibrium states
Introduction

Kinds of equilibrium
1. Stable equilibrium
2. Neutral equilibrium
3. Unstable equilibrium
4. Metastable equilibrium
Introduction

If ball is moved from its stable position it will rock back

Stable Equilibrium

If ball is moved from its stable position it will remain at a new


position
Neutral Equilibrium

If ball is moved from its position it will roll off the hill, until it
finds a stable point
Unstable Equilibrium

If ball is moved slightly from its stable position it will rock


back. But, moderated displacement will cause the ball to roll
down the other side of the hill Metastable Equilibrium
Introduction

Unstable Equilibrium
neither mechanics nor thermo knows, truly unstable equilibrium, equilibrium defined on
microscopic variables, large scale averages of quantities which on microscopic scale are subject to
fluctuations
Eg: Pressure exerted by a gas (macroscopic average of impulses from discrete molecular impacts)
Introduction

Stable Equilibrium Neutral Equilibrium Metastable Equilibrium

H2O vapors
H2O vapors H2 + O2
H2O liquid

A gas at constant T results A liquid + vapor at


to their initial states if Stable to small displacements
constant T Large compression leads to
displaced/released Vapor pressure depends raise in T that it could explode
on T
Introduction

•  A process that can be reversed in its direction by an


infinetesimal change in one or more of the state variables
is said to be a reversible process.
•  A classical example of this is the gas cylinder and piston.
If the pressure of the gas is say P atm and (p+dp) is
exerted from outside on the piston, the gas inside the
piston shall be compressed. However, if the external
pressure is (p-dp) then the gas shall expand.
Introduction

•  On the contrary a matchstick when it burns, the


process can not be reversed by changing one or
other parameters. Once burnt can not be
reproduced by reversing the process. This is
typically a Irreversible process.
•  Other examples are mixing of two gases, mixing
of two liquids to form a solution or flow of
electric current through resistor.
•  All natural processes are irreversible.
Introduction

Thermodynamic reversibility

Process must be “Quasi-Static”


Process must not have “Hysteresis”

To be quasi-static, a process must be carried out infinitely slowly that


every state through which the system passes may be considered as an
equilibrium state

Fast changes usually cause dis-equilibrium between the parts of the


system

Eg: Compression of gas, if carried out by sudden movement of the


piston, then sound waves or shock waves are setup in the gas and
change is not reversible
Introduction

Process must now have hysteresis

When a process is reversed in a system, the system does not


retrace its previous path but proceeds by a different one

Eg: Magnetisation of Iron


Thermodynamic equilibrium (TE)
•  A system is in (a) thermodynamic equilibrium (state) if it
undergoes no changes when isolated from its surroundings.
•  Given unchanging surroundings, the system will remain
unchanging if it is in equilibrium.
•  Equilibrium correspond to a state of balance; the system is “at
peace” with all its parts and with its surroundings.
•  Intuitively, non-equilibrium is identified from the existence of
“currents” or “flows” or “fluxes” such as heat flow, chemical
diffusion, electric currents etc. arising from certain “driving
forces” corresponding to the “imbalances” discussed above.
Thermodynamics studies the passage of system from one equilibrium state to another
equilibrium state. Often the passage itself is idealized using the concept of thermodynamic
Equilibrium (see later).
Introduction

•  Mechanical Equilibrium: if there is no pressure


gradient in the system.
•  Thermal Equilibrium: if there is no temperature
gradient in the system.
•  Chemical Equilibrium: if the rate of forward reaction
is equal to rate of backward reaction.
•  Complete thermodynamic equilibrium is thus that
situation where the system is in equilibrium with
respect to all such potentials like mechanical, thermal
and chemical.
Thermal equilibrium & Zeroth Law

Systems of constant mass and composition, requires only one pair of


independent variables for describing the state of the system

Lets take independent coordinates as X and Y


X- Generalised force
Y- Generalised displacement

Existence of equilibrium between two systems requires the state of the


system to remain constant

Existence of equilibrium depends on the boundary separating the two


systems
Thermal Equilibrium – two different boundaries
Thermal equilibrium & Zeroth Law
Adiabatic Boundary
Diathermic Boundary

If a wall is adiabatic, an If a wall is diathermic,


equilibrium state for system values of X, Y, X’, Y’
A may coexist with any Will change spontaneously
equilibrium state of B for until an equilibrium state of
all attainable values of the the combined system is
quantities X, Y, X’, Y’ reached
Thermal equilibrium & Zeroth Law
•  When a “hot” body is placed in contact with a “cold” body through a part
of their boundary that allows passage of heat, the properties of the body
change initially due to heat transfer between them. Eventually the heat
transfer stops and the properties no longer change with time. The two
bodies have reached thermal equilibrium.

The two systems are said to be in thermal equilibrium with one another
Thermal equilibrium & Zeroth Law
The two systems are said to be in thermal equilibrium with one another

•  Thermal equilibrium is the state achieved by two or more systems


characterized by restricted values of the coordinates of the systems,
after they have been in communication with each other through a
diathermic wall
Thermal equilibrium & Zeroth Law
Now imagine two systems A and B separated from each other by
adiabatic wall but each in contact simultaneously with a third system C
through diathermic walls and the whole system surrounded by adiabatic
walls
Thermal equilibrium & Zeroth Law
If, of three systems A, B and C:
•  system A is in thermal equilibrium with system C,
•  system B is in thermal equilibrium with system C,
Then:
systems A and B are in thermal equilibrium with each other.

Two systems in thermal equilibrium with a third are in


thermal equilibrium with each other

Reminder: “is in thermal equilibrium”è “no changes occur


when interaction is allowed between the systems through a
shared diathermal no-work boundary”
Thermal equilibrium & Zeroth Law
Temperature is a measure of hotness of a given macroscopic object,
as felt by a human body

Scientific understanding of the temperature builds upon thermal


equilibrium established in zeroth law of thermodynamics

Consider a system A in the state X1, Y1 in thermal equilibrium with


another system B in state X1’, Y1’

If system A is removed and its state is changed, there will be a


second state X2, Y2 that is in thermal equilibrium with the
original state of system B X1’, Y1’
Thermal equilibrium & Zeroth Law
All such states when plotted on XY diagram lie on a curve

An isotherm is the locus of all points representing states in which a


system is in thermal equilibrium with one state of another system
Thermal equilibrium & Zeroth Law

All the states of corresponding isotherms have something in common,


that they are in thermal equilibrium with one another

So the systems in these states may be said to possess a property that


ensures them being in thermal equilibrium with one another

This property is called as Temperature

The temperature of a system is a property that determines whether or not


a system is in thermal equilibrium with other systems

This property should be a scalar quantity


Zeroth Law : Implications

Device called Thermoscope

C In particular, system C may be as shown


in figure and have an easily measurable
property such as “mercury level” which
changes only in response to energy
interactions through diathermal no-work
walls.

Zeroth law can be restated:


“two systems A and B must be in thermal equilibrium if they have
resulted in the same mercury level on thermal contact with a standard
body C of the type shown in the figure”
Zeroth Law : Implications
•  “mercury level, as recorded by C” is a variable
characterizing thermal equilibrium just in the
same way pressure of a simple compressible
C system is a variable of “mechanical
equilibrium”.

•  To make sure that C does not significantly affect


states of A/B, C may be made “small enough”
in size compared to A/B. Then the mercury level
variable can be given the fancy name
temperature and considered the property of A/B
responsible for thermal equilibrium.

More generally, we can infer the existence of temperature


as a new property from the third law and concept of thermal
equilibrium, when both are expressed mathematically.
Specific Volume, Pressure & Temperature

If we want to know if two objects are at the same temperature, it is not necessary to bring them
into contact and see whether their observable properties change with time.

It is necessary only to see if they are individually in thermal equilibrium with a third object. The
third object is usually a thermometer.

Any object with at least one measurable property that changes as its temperature changes can be
used as a thermometer. Such a property is called a thermometric property

The particular substance that exhibits changes in the thermometric property is known as a
thermometric substance.
Specific Volume, Pressure & Temperature
20 Chapter 1 Getting Started

A familiar device for temperature measurement is the liquid-in-glass thermometer

Liquid

(a) (b) (c)

Liquid-in-glass Electrical-resistance
Fig. 1.13 Thermometers. (a) Liquid-in-glass. (b) Electrical-resistance. (c)Infrared-sensing
Infrared-sensing ear ear thermometer
thermometer.

Devices using conductors are known as resistance temperature detectors. Semiconduc-


tor types are called thermistors. A battery-powered electrical-resistance thermometer
As temperature increases, the liquid expands in volume and rises in the capillary. The length L
commonly used today is shown in Fig. 1.13b.
of the liquid in the capillary depends on the temperature
A variety of instruments measure temperature by sensing radiation, such as the
ear thermometer shown in Fig. 1.13c. They are known by terms such as radiation
thermometers and optical pyrometers. This type of thermometer differs from those
previously considered because it is not required to come in contact with an object to
determine its temperature, an advantage when dealing with moving objects or objects
Electrical resistance sensors are based on the fact that the electrical resistance of various
at extremely high temperatures.
materials changes in a predictable manner with temperature.
ENERGY & ENVIRONMENT The mercury-in-glass thermometer once
prevalent in home medicine cabinets and industrial settings is fast disappear-
ing because of toxicity of mercury and its harmful effects on humans. The
A variety of instruments measure temperature by sensing radiation, such as the ear
American Academy of Pediatrics has designated mercury as too toxic to be pres-
ent in the home. After 110 years of calibration service for mercury thermometers,
thermometer. They are known by terms such as radiation thermometers and optical pyrometers.
the National Institute of Standards and Technology (NIST) terminated this service in 2011 to
encourage industry to seek safer temperature measurement options. Alternative options for
home and industrial use include digital electronic thermometers, alcohol-in-glass thermom-
Temperature Scales

The tendency of the liquid in a glass thermometer to freeze at low temperatures imposes a
lower limit on the range of temperatures that can be measured. At high temperatures liquids
vaporize and therefore these temperatures also cannot be determined using glass thermometers

Several different thermometers might be required to cover a wide temperature interval

It is desirable to have a procedure for assigning temperature values that do not


depend on the properties of any particular substance or class of substances

Thermodynamic temperature scale.


Thermal equilibrium & Zeroth Law
•  To establish an empirical temperature scale, we select
some system with X-Y coordinates as a standard , and
adopt a set of rules assigning numerical value to
temperature associated
Choose any convenient path in the X-Y plane,
which intersects the isotherms at the same Y
coordinate but a different X Coordinate

Temperature associated with each isotherm is then


taken to be a convenient function of the X at the
intersection point

Coordinate X is called Thermometric property and the form of the


thermometric function t(x) determines the empirical temperature scale
Thermal equilibrium & Zeroth Law

Many different kinds of thermometers, each has its own thermometric


property

Let X stand for any one of the thermometric properties


Thermal equilibrium & Zeroth Law
Let us decide arbitrarily that the empirical temperature θ is directly
proportional to X to define the temperature scale

This equation applies in general to a thermometer placed in contact with


a system whose temperature θ(x) is to be measured.

It also applies when the thermometer is placed in contact with an


arbitrarily chosen standard state in a reproducible state

Such a state of an arbitrarily chosen standard system is called a fixed


point, that is a fixed temperature

The fixed point provides a reference temperature for the determination of


temperature scales
Thermal equilibrium & Zeroth Law
Before 1954, the international metric was based on the temperature
interval between two fixed points : Celsius scale

1.  Ice point


2.  Steam point

In 1954, a single fixed point was chosen


as the basis for a new international
temperature scale : Kelvin scale

Triple point of water

Very accurate and reproducible value of 273.16K


Thermal equilibrium & Zeroth Law

We can now solve this equation of the coefficient a

In general, the equation can be written as


Thermal equilibrium & Zeroth Law

For a constant volume thermometer

For a platinum wire resistor


Thermal equilibrium & Zeroth Law
For a Thermocouple
Thermal equilibrium & Zeroth Law
No thermometer compared in effectiveness with gas thermometer

Theoretical basis embodied in ideal gas law

The perfect gas temperature scale is based on the observation that


the temperature of a gas at constant volume increases
monotonically with pressure
the system whose temperature is to be measured. The mercury column is so
el of mercury stands at the reference mark S . This ensures that the volume of
Thermal equilibrium & Zeroth Law
a constant value. Let the pressure of the gas be read as P. Let a similar
de when the gas bulb is maintained at the triple point of water, Ptp. We can
putting water and ice in an insulated chamber and evacuating air ( which is then
Objectives_template 10/04

pour). 273.16 ( P/ P tp ) as a function of the pressure at the triple point, results in a curve as shown in figure
5.5.

Figure 5.5

Figure 5.4 When these curves are extrapolated to zero pressure, all of them yield the same intercept. This
behaviour can be expected since all gases behave like ideal gas when their pressure approaches
zero. The correct temperature of the system can be obtained only when the gas behaves like an
ideal gas, and hence the value is to be calculated in limit Ptp 0. Therefore
he triple point of water has been assigned a value of 273.16 K. Since for an
P, , as
Rankine & Fahrenheit Temperature Scales

The Rankine scale, the unit of which is the degree rankine ( R), is
proportional to the Kelvin temperature according to

The Rankine scale is also an absolute thermodynamic scale with an


absolute zero that coincides with the absolute zero of the Kelvin scale.

In thermodynamic relationships, temperature is always in terms of the


Kelvin or Rankine scale unless specifically stated otherwise.
Temperature Scales

The Celsius temperature scale uses the unit degree Celsius (8C), which has the same magnitude
as the kelvin

The zero point on the Celsius scale is shifted to 273.15 K

T( C) = T( K) - 273.15

On the Celsius scale the triple point of water is 0.01 C and that 0 K corresponds to −273.15 C

A degree of the same size as that on the Rankine scale is used in the Fahrenheit scale, but the
zero point is shifted according to the relation

Fahrenheit temperature of the ice point (0 C) is 32 F and of the steam point (100 C) is 212 F
assigned to the easily reproducible triple point of water: the state of equilibrium
Temperature Scales

K °C °R °F

373.15

671.67
100.0

212
Steam point

Triple point
273.16

491.69

32.02
of water

0.01
273.15

0.00

491.67

32.0
Ice point

Fahrenheit
Rankine
Celsius
Kelvin

–273.15

–459.67
0.00

0.00

Absolute zero

Fig. 1.14 Comparison of


temperature scales.
MM209 - Thermodynamics
Instructor : Aswani Yella
Work
If a system undergoes displacement under the action of force, work is said to be done

And the amount of work being equal to the product of force and displacement

If a system as a whole exerts force on its surroundings and a displacement takes place, the work
that is done either by the system or on the system is called external work

Eg: Gas confined in a cylinder and at a uniform pressure, while expanding and imparting motion
to a piston does external work on its surroundings

The work done however by one part of a system on another part is called internal work
Eg: Interactions of molecules, atoms or electrons on one another constitute internal work
Work
Internal work Not dealt in Macroscopic thermodynamics

Only work that involves an interaction between a system and its surroundings is analyzed

Work in changing the volume of a Hydrostatic system

Hydrostatic system: Closed cylinder equipped with a frictionless movable piston on which the
system and the surroundings may act.

Cross sectional area: A


Pressure exerted by the system at the piston face is P
Force on the internal surface of the piston = PA

Now if apply an external force on the piston that the piston moves in an infinitesimal distance dx
during compression, then the surroundings perform an infinitesimal amount of work dW

dW=Fdx= PAdx

During compression volume of system decreasing so Adx=-dV


Work

The presence of minus sign before PdV ensures that a negative dV gives rise to positive work
done on the system

A positive dV yields negative work done by the system

In a finite quasistatic process in the which the volume changes from Vi to Vf, the amount of work
done by the system is

If the change in volume is performed quasi-statically, the system pressure P is at all times equal to
the external pressure and it is also a thermodynamic coordinate

Which means we can express it as a function of T and V


Work
As the volume of hydrostatic system changes because of the motion of a piston in a cylinder, the
position of the piston at any moment is proportional to volume

We can draw a PV diagram by following the motion of the piston and the pressure

Pressure and the volume changes of a gas during expansion can be indicated as a curve on PV
diagram
Work
The integral for this process is evidently the shaded area under curve I which represents the work

If we carry out compression of the gas the work is represented by the shaded area under curve II

According to the sign convention for work, work is done by the system in curve I and work is
done on the system in curve II
Work
Hydrostatic work depends on the path

I to a to f work done is equal to -2PoVo


I to b to f work done is equal to –PoVo
I to f work done is equal to -3/2PoVo

Work done by a system not


only depends on the initial and
final states but also on the path
of integration

Another way of saying that


for a quasi-static process the
expression cannot be
integrated until P is specified
as a function of V using
appropriate equation of state
Work
Energy
Energy is often defined as the capacity to produce work

The capacity represents a combination of an effort and the change brought about by the effort.

The effort involved is measured quantitatively as a "driving force" in thermodynamics

The quantitative value of this change is called a "displacement".

The product of a driving force and its associated displacement represents a quantity of energy,
but in thermodynamics this quantity has meaning only in relation to a specifically defined
system.

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.

The displacement could also occur within the system but the driving force is a property of the
surroundings and is applied externally at the system boundary.
body is

Energy
Objectives_template 10/04/17, 17:41

Macroscopic modes
Module 1 : of energy
The work done on a body in accelerating it from its initial velocity to a final velocity , is equal
Lecture 3to: Energy
the change
and in the kinetic energy of the body. If the body is decelerated from a velocity
Processes to a
velocity by the application of resisting force, the work done by the body is equal to decrease in its
Kinetic energy kinetic energy.modes of energy
Macroscopic
Potential energy Potential Energy
Kinetic Energy (KE)(PE)
A body of mass m is moved from an initial elevant Z1 to a final elevation Z2(Fig
3.1)
If a body is accelerated from its initial velocity to final velocity , the total work done on the
If a body is accelerated from its initial velocity to final velocity, the total work done on the body
body is
is

The work done on a body in accelerating it from its initial velocity to a final velocity , is equal
to the change in the kinetic
The workenergy of the
done on a body body. it from its initial velocity to a final velocity , is equal
in accelerating
to the change in the kinetic energy of the body. If the body is decelerated from a velocity to a
velocity by the application of resisting force, the work done by the body is equal to decrease in its
If the body is decelerated
kinetic from
energy. a velocity to a velocity by the application of resisting force, the

work done by the body is equal Potentialto decrease


Energy (PE) in its kinetic energy.
A Figure mass m is moved from an initial elevant Z1 to a final elevation Z2(Fig
body of 3.1
3.1)
The force on the body, F = mg
This force has moved a distance ( Z2 - Z1) . Therefore, the work done on the
A body of mass m is moved from an initial elevant Z1 to a final elevation Z2
body

The kinetic energy and potential energy are also called organized form of energy that can be
readily converted into work.
The kinetic energy and potential energy are also called organized form of energy that can be readily
converted into work.
Module 1 :
Lecture 3 : Energy and Processes
Energy
Microscopic modes of
Microscopic energy of energy
modes
TheThe
microscopic modesmodes
microscopic of energy
of refer to the
energy energy
refer stored
to the in the stored
energy molecular and molecular
in the atomic and ato
structure of the system.
the system.
The molecules are in random motion. A molecule possesses energy in several forms.
The molecules are in random motion. A molecule possesses energy in several forms
•  Translational energy, Rotational energy, Vibrational energy
•  Electronic energy, Chemical
Translational energy,
energy, Nuclear energy
Rotational energy, Vibrational energy.
Electronic energy, Chemical energy, Nuclear energy.

If ε Ifrepresents energyenergy
ε represents of one molecule, then
of one molecule, then

Random motions or disorganized motions of molecules

One ofIf the


N major
is thetasks
totalinvolved
number in of molecules inis the
thermodynamics system,
devising meansthen the total amount of micr
for converting
energyenergy into useful or organized work
disorganized
U=Nε
Relationship between work & heat
There are other means of changing the state of the system that do not necessarily involve the
performance of work

Consider four different processes which involve closed systems

System 1 consisting of water and a paddle wheel, which is used


to rotate and churn the water by means of a falling weight

As a result the temperature of the water rises from room


temperature to slightly higher temperature
Relationship between work & heat
Consider four different processes which involve closed systems

System 2 consists of water and a resistor and the electric current in


the resistor being maintained by a generator turned by means of a
falling weight

Again the temperature of the water increases

In both system 1 and system 2 the state of the system is caused to change and the agency for
changing the state of the system is the falling weight

Both processes involve performance of work


Relationship between work & heat
Consider four different processes which involve closed systems

System 3 consists of water in a diathermic container which is


in contact with the burning gases at a high temperature

System 4 consists of water in a diathermic container but now


the system is near by but not in contact with a lamp whose
temperature is higher than that of water

In both the cases system is caused to change but in neither case


the agency of change cannot be described by mechanical means
Relationship between work & heat
Upto the beginning of the 19th century such a phenomena were explained by postulating the
existence of a substance termed caloric, an elastic fluid found in every body

In the caloric theory of heat, the temperature of a substance was considered to be determined by
the quantity of caloric gas which it contained, and two bodies of differing temperature, when
placed in contact with one another, came to an intermediate common temperature as the result of
caloric flowing between them

Body at high temperature contained more caloric and the one at a low temperature had only
little caloric
Relationship between work & heat
The relation between heat and work was first suggested in 1798 by Count Rumford

During the boring of cannon at the Munich Arsenal, noticed that the heat produced during the
boring was roughly proportional to the work performed during the boring

Until then heat had been regarded as being an invisible fluid called caloric which resided
between the constituent particles of a substance.

Rumford’s observation that heat production accompanied the performance of work was
accounted for by the caloric theory as being due to the fact that the amount of caloric which
could be contained by a body, per unit mass of the body, depended on the mass of the body

Small pieces of metal (the metal turnings produced


by the boring) contained less caloric per unit mass
than did the original large mass of metal, and thus,
in reducing the original large mass to a number of
smaller pieces, caloric was evolved as sensible heat
Relationship between work & heat
Rumford then demonstrated that when a blunt borer was used (which produced very few metal
turnings), the same heat production accompanied the same expenditure of work

The caloric theory “explained” the heat


production in this case as being due to the action
of air on the metal surfaces during the
performance of work.

The caloric theory was finally discredited in 1799


when Humphrey Davy melted two blocks of ice by
rubbing them together in a vacuum

In this experiment the latent heat necessary to melt the ice was provided by the mechanical work
performed in rubbing the blocks together.
Adiabatic work – Joules Experiments
When a closed system is completely surrounded by an adiabatic boundary and the system is
coupled with the surroundings so that work can be done, then the work is called Adiabatic
work
Adiabatic work – Joules Experiments
Lets take the initial state characterized by thermodynamic
coordinates Pi =1 atm and Ti=287.7K
and the final state by the coordinates Pf =1 atm and Tf = 288.7K

i to f Path I
i to a to b to f Path II
i to c to d to f Path III

We can have infinite number of paths by which the


system may be transferred from an initial state to final
state i to f by the performance of adiabatic work only
Adiabatic work – Joules Experiments

Joule found out that irrespective of the path that is


followed, the adiabatic work is same along all
such paths

Passing electric current through a coil


immersed in the water
Rotating a paddle wheel immersed in the water
Compressing a cylinder of gas immersed in the
water
Rubbing together two metal blocks immersed
in the water
Adiabatic work – Joules Experiments
Joule conducted experiments in which work was performed in a certain quantity of
adiabatically contained water and measured the resultant increase in the temperature of the
water.

If friction in mechanism is
negligible, the work done
by the paddle wheel on the
water equals the change of
potential energy of the
weights.

Rotating a paddle wheel immersed in the water Passing electric current through a coil
immersed in the water
As the weights fall at constant speed,
they turn a paddle wheel, which does Electrical work is done on the system by the
work on water. generator, which is driven by the falling weight.

A direct proportionality existed between the work done and the resultant increase in temperature
and that the same proportionality existed no matter what means were employed in the work
production
Adiabatic work – Joules Experiments
From the Joules experiments, we can generalize and frame a restricted statement called the
First law of Thermodynamics

If a closed system is caused to change from an initial state to a final state by adiabatic means
only, then the work done on the system is the same for all adiabatic paths connecting the two
states

In Mechanics, in moving an object from one point to another point in gravitational field, in the
absence of friction the work done depends only on the positions of the two points and not on the
path through which the body was moved

For a conservative force, there exists a function of the space coordinates of the body whose final
value minus initial value is equal to work done and this function is called potential energy
function

Similarly the work done in moving an electric charge from one point to another in a conservative
electric field is independent of the path and the function is called electric potential function
First law of Thermodynamics
From the Joules experiments, we can generalize and frame a restricted statement called the
First law of Thermodynamics

If a closed system is caused to change from an initial state to a final state by adiabatic means
only, then the work done on the system is the same for all adiabatic paths connecting the two
states

From this restricted statement that we defined, there exists a function of the coordinates of the
thermodynamic system whose value at the final state minus initial state is equal to the
adiabatic work in going from one state to another

This function is called as internal energy function

Denoting internal energy function by U, we can write


Internal Energy
Denoting internal energy function by U, we can write

If work is done on the system, Uf will be greater than Ui

The physical interpretation of the difference Uf-Ui is the increase in the internal energy of the
system

The importance of this equation is that thermodynamic work which is generally path dependent
becomes path independent for an adiabatic process

The equality of the increase in the internal energy and the adiabatic work expresses the law of
conservation of energy

The internal energy is a function of as many thermodynamic coordinates as are necessary to


specify the state of the system
Internal Energy
The equilibrium states of a closed hydrostatic system can be described by means of two of the
three thermodynamic coordinates P, V, T

So internal energy can be also thought of as function of any two of the three thermodynamic
coordinates

Exact form of the function of U is unknown but it is not necessary to know the exact form of the
internal energy function

Only need to know that such a function exists as a result of experiments of adiabatic work

If the coordinates characterizing the two states differ from each other only infinitesimally then the
change in the internal energy can be written as dU

U is a state function and hence dU should be an exact differential

Integral of dU is independent of the path between initial and final states


Internal Energy
In the case of a hydrostatic system, if U is regarded as a function of T and V then

if U is regarded as a function of T and P then

if U is regarded as a function of V and P then

Note: The derivatives are not equal because the function U is not the
same in both the cases

is a function of T and V
is a function of T and P
The internal energy is an extensive property of a system (Section F.3) and is mea-
sured in joules (1 J = 1 kg m2 s−2, Section F.4). The molar internal energy, Um, is the
Internal Energy
internal energy divided by the amount of substance in a system, Um = U/n; it is an
intensive property and commonly reported in kilojoules per mole (kJ mol−1).
Molecular interpretation of internal energy
(a) Molecular interpretation of internal energy
A molecule has a certain number of motional degrees of freedom, such as the ability to
A motion
translate (the moleculeofhas
itsacentre
certainofnumber of motional
mass through degrees
space), of freedom,
rotate around itssuch as the
centre of ability
mass, or
to translate
vibrate (as its (the motion
bond lengths of itschange,
and angles centre ofleaving
mass through space),
its centre rotateunmoved)
of mass around its centre
of mass, or vibrate (as its bond lengths and angles change, leaving its centre of mass
unmoved). Many physical and chemical properties depend on the energy associated
with each of these modes of motion. For example, a chemical bond might break if a lot
Accordingoftoenergy becomestheorem,
equipartition concentrated in it, for instance
the average as each
energy of vigorous vibration.
quadratic contribution to the
energy is 1/2The
kT. ‘equipartition theorem’ of classical mechanics was introduced in Section F.5.
According to it, the average energy of each quadratic contribution to the energy is
1
2
kT. As we saw in Section F.5, the mean energy of the atoms free to move in three
the mean energy of theis atoms
dimensions 3
kT free
and theto move
total in three
energy of a dimensionsperfect
monatomic is 32 gas
kT is
and
3 the total
NkT, or 3 energy of a
nRT
2 2 2
monatomic(because
perfect Ngas
= nNis 3/2 NkT, or 3/2 nRT
A and R = NAk). We can therefore write

Um(T) = Um(0) + 32 RT (monatomic gas; translation only) (2.2a)

where Um(0) is the molar internal energy at T = 0, when all translational motion
where Um(0)hasis ceased
the molar
andinternal
the sole energy at T =to0,the
contribution when all translational
internal energy arisesmotion
from thehasinternal
ceased and
the sole contribution to the internal
structure of energy
atoms. This arises shows
equation from the
thatinternal structure
the internal of the
energy of aatoms.
perfect
gas increases linearly with temperature. At 25°C, 32 RT = 3.7 kJ mol−1, so translational
This equation shows
motion that the internal
contributes kJ mol−1oftoathe
about 4 energy perfect
molargas increases
internal energylinearly with sample
of a gaseous temperature.
At 25°C, 3/2ofRT = 3.7
atoms or kJ mol−1, so translational motion contributes about 4 kJ mol−1 to the
molecules.
molar internal When
energythe
of gas
a gaseous
consistssample of atoms
of molecules, weorneed
molecules.
to take into account the effect of
Internal Energy
48 2 THE FIRST LAW
When the gas consists of molecules, we need to take into account the effect of
rotation and vibration
1
kT
U
2
A linear molecule, such as N2 and CO2, can rotate around
An
two axes perpendicular to the line of the atoms, so it has two
eac
rotational modes of motion, each contributing a term 1/2 kT
to the internal energy mea
1 mo
2 kT
The mean rotational energy is kT and the rotational contribution to Um
the molar internal energy is RT (a)
1
2 kT The
5
Um(T) Um=
Um=(T) 5
2
RT+
(0)U+m(0) RT (linear molecule; translation and rotation(2.2b)
2 (linear molecule; translation and rotation only)
only) (2.2b) the
mo
A nonlinear
A nonlinear molecule,
molecule, such as such
CHasas CH
4 or H24O,orcanH2O, canaround
rotate rotate three
around three
axes and,axes and, again,
again,
A nonlinear molecule, such CH4 or H2O, 1 can rotate as m
each
modemode
eacharound of of motion
motion contributes
contributes a term a12 term
kT to kTinternal
2the
to the internal energy. Therefore,
energy. Therefore, the the
three axes and,3 again,3 each mode of motion 3 3 1 per
meanmean rotational
rotational energyenergy
is 2 kTisandkT and
there isthere
a is a
rotationalrotational contribution
contribution of RT of
to theRT to the kT
contributes a term 1/2 kT to2 the internal energy 1
2 2 2
inte
molar internal
molar energy.
internal That is,
energy. That is, (b) 2 kT
logi
Um=(T)
Um(T) Um=(0)U+ (0)
m
3RT+ 3RT
(nonlinear molecule;
(nonlinear translation
molecule; and rotation
translation only) (2.2c)
and rotation only) (2.2c) N
Fig. 2.5 The rotational modes of molecules the
TheThe
internal
The energy
internal
internal nownow
energy
energy increases twicetwice
nowincreases
increases astwice
rapidly with temperature
asasrapidly
rapidly with compared
withtemperature
temperature
and the with average
compared
compared
corresponding with the
withenergies at a
themonatomic
monatomicgasgas. Put another way: for a gas consisting oftemperature
1 mol of nonlinear betw
the monatomic gas. Put another way: for a gas consisting T. (a)ofA linear
of 1 mol molecule can
nonlinear
molecules to undergo the same rise in temperature as 1 mol of monatomic gas, twice perf
Internal Energy
It consists of
•  macroscopic kinetic energy due to motion of the system as a whole.
•  potential energy of the system due to its position in the force field.
•  kinetic energy of atoms and molecules in the form of translation, rotation and vibration.
•  energy of interaction amongst atoms and molecules
•  columbic energy of interaction amongst electrons and nucleii in atoms
•  energy contents of the electrons and nucleii of atoms

•  In conventional chemical thermodynamics which we shall be concerned with only kinetic


energies of atoms and molecules and interaction amongst atoms and molecules i. e. items (3)
and (4) are considered to be important since changes occurring in them principally contribute
to ΔU.

•  Absolute value of the energy is not known. All we can determine is change in internal energy.
•  Internal energy will depend on temperature for a material of fixed mass, composition and
structure.
•  U is function of Temperature only.
Energy Fig. 1‐4: Forms of energy. 
Diathermal Work, Heat & 1st law of Thermodynamics

So far we have been considering processes during which the system undergoes a change of state
through the performance of adiabatic work only

Gas in thermal contact Magnetization of a solid


with a flame in contact with liquid
Helium

Now imagine two different experiments performed on the same closed system one
adiabatically and the other diathermically

Experiments show that the work done diathermically is not equal to Uf-Ui
Diathermal Work, Heat & 1st law of Thermodynamics
Now imagine two different experiments performed on the same closed system one
adiabatically and the other diathermically

Experiments show that the work done diathermically is not equal to Uf-Ui

Inorder to be consistent with the law of conservation of energy, we are forced to conclude that
energy has been transferred by means of other than performance of work

This energy which has taken place only by virtue of the temperature difference between the
system and the surroundings is called as Heat

When a closed system whose surroundings are at a different temperature and on which the
diathermic work may be done, then the energy transferred by non mechanical means is
called Heat

Denoting heat by Q, we have


Heat and Work
FIRST LAW
Surroundings

Surroundings
Surroundings

Surroundings
Energy

Energy

Energy

Energy

Energy

Energy
Energy

Energy

Energy

Energy

Energy

Energy
hermic
mic
ess Exothermic
process System System
System System
(b) When energy is transferred to the
Fig. 2.3 Fig. 2.4 When a system does work,

Whensurroundings
energy as heat,
is Fig. the
2.3 transfer
transferred When to the
energy it stimulates
is transferred to the orderly motion
Fig. 2.4inWhen
the a system does work,
stimulates randomsurroundings
motion of the as atoms
heat,inthe transfer itWhen
surroundings. For instance, a system
the atoms
stimulates doesinwork,
orderly motion the
surroundings as heat, the
the surroundings. stimulates transfer
Transfer of random
energy from stimulates
shown here may be part of a weight that is
motion of the atoms in it motion
stimulates
surroundings. For orderly motion
instance, the atoms in the
random motion ofthethe
the surroundings to the atoms in Transfer
system makes
surroundings. the of energy from
use being raised. The ordered of the
shown here may be part of a weight that is
of random motion (thermal motion) in the atoms in a falling weightsurroundings.
does work on the For instance, the atoms
surroundings.
surroundings.Transfer of energy from the
the surroundings to the system makes use being raised. The ordered motion of the
of random motion (thermal motion) in the
system. shown here may be part of a weight that
atoms in a falling weight does work on the is
surroundings to the system makes use of
surroundings. being raised. The ordered motion
system. of the
hermic random motion (thermal motion) in the
Heat
ess atoms in a falling weight does work on the
surroundings.
mic Exothermic system.
(b) The molecular interpretation of heat and work
process
ic process(d) In molecular terms, heating is the transfer of energy that makes use of disorderly
he molecular motion(b)inThe molecular interpretation
the surroundings. The disorderlyof heat and
motion work is called
of molecules
This equation is known as the Mathematical formulation of the first law of thermodynamics

Like internal energy and work heat is measured in Joules in the SI system

For a process involving only infinitesimal changes in thermodynamic coordinates of a system the
general statement

Exact differential dU is the sum of two inexact differentials dQ and dW

dU is a property within the system


dQ and dW are not related to the properties of the system but they refer to how the surroundings
interact with the system by means of processes transferring energy
Statement of First law
For an infinetesimal process, the statement is:
dU = δq – δW
Sum of all forms of energy exchanged by a system with its surrounding is equal to the
change in internal energy of the system which is a function of state .

Energy can neither be created nor can be destroyed

The total energy of a system and its surroundings shall be constant and that it may change its
forms or may exchange between themselves'.

There exists for every thermodynamic system a property called the energy. The change of
energy of a system is equal to the mechanical work done on the system in an adiabatic process.
In a non-adiabatic process, the change in energy is equal to the heat added to the system minus
the mechanical work done by the system.
Significance of the First Law

•  It is based on the law of conservation of energy.

•  It brought in the concept of the internal energy.

•  It separates heat and work interactions between the system and surroundings as two different
terms.

•  It treats internal energy as a state property is an exact differential.


For an infinitesimal quasi-static process of a hydrostatic system, the first law can be written as

Where U is a function of any two of the three thermodynamic coordinates P, V, T


Composite system consisting of two hydrostatic parts, separated by a diathermic wall then

In the case of a composite paramagnetic gas


MM209 - Thermodynamics
Instructor : Aswani Yella
Statement of First law
For an infinetesimal process, the statement is:
dU = δq – δW
Sum of all forms of energy exchanged by a system with its surrounding is equal to the
change in internal energy of the system which is a function of state .

Energy can neither be created nor can be destroyed

The total energy of a system and its surroundings shall be constant and that it may change its
forms or may exchange between themselves'.

“There exists for every thermodynamic system a property called the energy. The change of
energy of a system is equal to the mechanical work done on the system in an adiabatic process.
In a non-adiabatic process, the change in energy is equal to the heat added to the system minus
the mechanical work done by the system.”
Heat Capacity

From the mathematical form of first law, we saw that internal energy can be changed either
by heat or work

When systematic experiments were performed to measure the capability of a substance to store
internal energy, heat rather than work is used

2.4 HEAT TRANSACTIONS


The results came55 to be known as the heat capacity of the sample

increase
esent we
The term heat capacity implies that a substance can hold heat
Internal energy, U

n a con- B
, then a but it is false
curve at
The heat
Heat is not a function of thermodynamic state of a system,
A
internal energy is!
So the proper expression should be Internal energy capacity
[2.15]
Temperature, T
e of the
volume Fig. 2.10 The internal energy of a system
Heat Capacity

•  In chemical and metallurgical processes, materials get heated or cooled and therefore it is
necessary to know the amount of heat required to heat or amount of heat liberated on cooling
a material over a certain temperature range.
•  Different materials require different amounts of heat to get heated through the same
temperature rise. This is because the materials have different heat capacities.
•  This is so because of the variation in the crystal structure of the materials and their related
parameters.
Heat Capacity
When heat is absorbed by a system, a change of temperature may or may not take place,
depending on the state of the system, eg., at the melting temperature

If a system experiences a change of temperature from Ti to Tf during transfer of Q units of heat,


the average heat capacity of a system is defined as the ratio

As both Q and Tf-Ti become smaller, this ratio approaches a limiting value known as the
heat capacity denoted by C

Heat capacity is measured in Joules per Kelvin in SI units


Heat Capacity
Is heat capacity an extensive quantity or an intensive quantity?

Heat capacity is an extensive quantity

specific heat capacity is an intensive quantity measured in Joules per kilogram - Kelvin

Usually heat capacities are standardized to the same amount of substance called mole

If C is the heat capacity of n moles, then molar heat capacity c is given by

Joules per mole - Kelvin

Heat capacity may be negative, zero, positive or infinite depending on the process the system
undergoes during the heat transfer
Heat Capacity
In the case of a hydrostatic system the ratio dQ/dT has a unique value each time a measurement
is made while the pressure is held constant
Under these conditions, C is called heat capacity at constant pressure and is denoted by Cp

In general Cp is a function of P and T

Similarly, the heat capacity at constant volume is the result while volume is held constant

Cv is a function of V and T

In general, Cp and Cv are different


Heat Capacity
Each heat capacity of a simple system is function of two variables
Heat Capacity
The mathematical formulation of first law for hydrostatic system is
Heat Capacity
Heat Capacity

If heat is added at constant If heat is added at constant pressure the heat


volume, no work is done, so energy transferred will be used to expand the
the heat added equals the substance and to increase the internal energy.
increase in Internal energy
Measurement of Heat Capacity
The unit of heat found most convenient was called calorie defined as the heat required to raise
the temperature by 1oC in a system of 1g of water

Later on it was found out that heat necessary to change 1g of water from 0 to 1oC was
different from that of the heat required to go from, say 30 to 31oC.

When the measurements became precise the calorie is defined as the heat needed for 1g of
water to go from 14.5oC to 15.5oC

The amount of work that had to be dissipated in


water per unit mass of water in going from
14.5oC to 15.5oC was called the mechanical
equivalent of heat, which was measured to be
4.1860 J/cal

Specific heat of water


Measurement of Heat Capacity
Calorimetry is the study of heat transfer during physical and chemical processes.

A calorimeter is a device for measuring energy transferred as heat

The most common device for measuring ∆U is an adiabatic bomb calorimeter


54 2 THE FIRST LAW

Firing Thermometer syste


Oxygen
leads is al
A constant-volume bomb calorimeter. The ‘bomb’ is the input
elect
central vessel, which is strong enough to withstand high Bomb circu
pressures. Sample

The calorimeter (for which the heat capacity must be Oxygen d


under
known) is the entire assembly shown here. pressure
We
To ensure adiabaticity, the calorimeter is immersed in a Water cons
water bath with a temperature continuously readjusted to ∆
that of the calorimeter at each stage of the combustion.
It fo
Fig. 2.9A constant-volume bomb
(qV >
calorimeter. The ‘bomb’ is the central
vessel, which is strong enough to withstand in fa
Measurement of Heat Capacity
The change in temperature, ∆T, of the calorimeter is proportional to the energy that the reaction
releases or absorbs as heat.

Therefore, by measuring ∆T we can determine qV and hence find ∆U.

The conversion of ∆T to qV is best achieved by calibrating the calorimeter using a process of


known energy output and determining the calorimeter constant, the constant C in the relation
q = C∆T

The calorimeter constant may be measured electrically by passing a constant current, I, from a
source of known potential difference, ∆φ, through a heater for a known period of time, t, for then
q = It∆φ

Alternatively, C may be determined by burning a known mass of substance (benzoic acid is


often used) that has a known heat output. With C known, it is simple to interpret an observed
temperature rise as a release of heat.
Enthalpy
•  If pressure is maintained constant during change of system
from state I to state II the work done
II II
w= ∫ PdV = P ∫ dV = P (VII − VI )
I I

From the first law:


UII – UI = δq – P(VII – VI )
On rearranging these terms
(UII + PVII ) - (UI + PVI ) = δq
Or HII - Hi = ΔH = δq
Where H = U + PV is called enthalpy. The heat content at
constant pressure is called enthalpy.
Enthalpy
•  Enthalpy is a state property but heat is not.
As we know H = U + PV
dH = dU + PdV + VdP
As U is a function of state so one can write
⎛ ∂U ⎞ ⎛ ∂U ⎞
dU = ⎜ ⎟ dP + ⎜ ⎟ dV
⎝ ∂ P ⎠V ⎝ ∂V ⎠P
⎡ ⎛ ∂U ⎞ ⎤ ⎡ ⎛ ∂U ⎞ ⎤
Hence dH = ⎢V + ⎜ ⎟ ⎥ dP + ⎢ P + ⎜ ⎟ ⎥ dV
⎣ ⎝ ∂ P ⎠V ⎦ ⎣ ⎝ ∂V ⎠P ⎦

= M dP + N dV (Say)
Enthalpy
⎡ ⎛ ∂U ⎞ ⎤ ⎡ ⎛ ∂U ⎞ ⎤
M = ⎢V + ⎜ ⎟ ⎥ , N = ⎢P + ⎜ ⎟ ⎥
⎣ ⎝ ∂ P ⎠V ⎦ ⎣ ⎝ ∂V ⎠P ⎦

•  Differential of coefficient of dP w.r.t V at constant P is given by the relation

⎛∂M ⎞ ⎛ ∂2 U ⎞
⎜⎜ ⎟⎟ = 1 + ⎜⎜ ⎟⎟
⎝ ∂V ⎠ ⎝ ∂ V∂ P ⎠
•  Differential of coefficient of dV w.r.t P at constant V is given by the relation

⎛∂N ⎞ ⎛ ∂2 U ⎞
⎜⎜ ⎟⎟ = 1 + ⎜⎜ ⎟⎟
⎝ ∂P ⎠ ⎝ ∂ P∂ V ⎠
•  Hence the above two partial differentials are equal proving thereby that the
equation for dH is an exact differential equation and thus leading to the
conclusion that H is a function of state.
Enthalpy
•  As Internal energy of an ideal gas is a function of
temperature only.
•  At constant temperature dT = 0 and therefore dU =
0 so ⎛ ∂U ⎞
⎜⎜ ⎟⎟ = 0
⎝ ∂ P ⎠T

•  As we know: H = U + PV

⎛∂H⎞ ⎛∂U⎞ ⎡ ∂(P V )⎤


⎜⎜ ⎟⎟ = ⎜⎜ ⎟⎟ + ⎢ ⎥
⎝ ∂ P ⎠T ⎝ ∂ P ⎠T ⎣ ∂ P ⎦T

•  For an ideal gas at Constant T, PV = constant, d


(PV) = 0
Enthalpy

⎛∂H⎞ ⎛ ∂U ⎞
⎜⎜ ⎟⎟ = ⎜⎜ ⎟⎟ = 0
⎝ ∂ P ⎠T ⎝ ∂ P ⎠T

Enthalpy of an ideal gas is independent of pressure


at constant temperature.
Similarly, enthalpy is independent of volume.
Hence H is a function of T only for the fixed mass
of the substance.
Internal Energy Vs Enthalpy
•  Internal energy is all that energy stored in the system. But, What does enthalpy
mean? This can best illustrated by the example of calcination of calcium carbonate
and calcium silicate.
Ca2SiO4 = 2CaO + SiO2
CaCO3 = CaO + CO2

•  The enthalpy change of the process will be equal to invested bond energy to break
the bond between CaO and SiO2 or internal since both CaO and SiO2 are solids.
•  But in the 2nd case CO2 is a gas then breaking of one mole of CaCO3 results in the
formation of 22.4 ltrs. of CO2.
•  Because of the generation of 22.4L of CO2, expansion in volume will take place.
•  In this process of expansion, the system will do work equivalent to ∫ PdV as
mechanical work on the surrounding.
Internal Energy Vs Enthalpy
•  Hence in addition to the requirement of energy for breaking the bond of
CaO-CO2 additional energy equivalent to ∫ PdV will have to be supplied to
the system making a total of U + ∫ PdV and this is the enthalpy change of
the system on calcination.
•  For chemical processes where there is no significant change in volume as
in
Ca2SiO4 = 2CaO + SiO2
•  The ∫ PdV is practically absent and U and H are almost the same.
•  In chemical and metallurgical world, even if term ∫ PdV is absent, it
worthwhile to refer to H which is more appropriate.
Heat Capacity
From the mathematical definition of enthalpy, we can write

H = U + PV

Differentiating gives dH = dU + PdV + VdP

From the 1st law of thermodynamics we know that dq = dU + PdV

Substituting this we get

dH = dq + VdP

At a constant Pressure dP =0

This implies that dH = dq at a constant pressure

Dividing this by dT we end up getting ⎛ dH ⎞ ⎛ dq ⎞


⎜ ⎟ =⎜ ⎟
⎝ dT ⎠ p ⎝ dT ⎠ p
Heat Capacity

Molar heat capacity at constant pressure is given by


⎛δ q ⎞ ⎛ ∂H ⎞
CP = ⎜⎜ ⎟⎟ = ⎜⎜ ⎟⎟
⎝ ∂ T ⎠P ⎝ ∂ T ⎠P
Since at constant pressure δq = dH. Further we can write
dH = CP dT
Or H T2 − H T1 =
T2
C P dT
∫ T1

CP > CV since CP includes heat required to do work against


pressure also besides raising temperature
Interrelationship of CP and CV
⎛ ∂H ⎞ ⎛ ∂U ⎞ ⎛ ∂ (U + PV ) ⎞ ⎛ ∂U ⎞
C P − CV = ⎜
⎜ ⎟
⎟ ⎜
−⎜ ⎟
⎟ ⎜
=⎜ ⎟
⎟ − ⎜⎜ ⎟⎟
⎝ ∂ T ⎠ P ⎝ ∂ T ⎠V ⎝ ∂T ⎠V ⎝ ∂ T ⎠V
⎛ ∂U ⎞ ⎛ ∂U ⎞ ⎛ ∂V ⎞
= ⎜⎜ ⎟⎟ − ⎜⎜ ⎟⎟ + P ⎜⎜ ⎟⎟
⎝ ∂ T ⎠ P ⎝ ∂ T ⎠V ⎝ ∂T ⎠P

And we know ⎛ ∂U ⎞ ⎛ ∂U ⎞
dU = ⎜⎜ ⎟⎟ dV + ⎜⎜ ⎟⎟ dT
⎝ ∂ V ⎠T ⎝ ∂ T ⎠V

differentiating w.r.t T at constant P we get

⎛ ∂U ⎞ ⎛ ∂U ⎞ ⎛ ∂V ⎞ ⎛ ∂U ⎞
⎜⎜ ⎟⎟ = ⎜⎜ ⎟⎟ ⎜⎜ ⎟⎟ + ⎜⎜ ⎟⎟
⎝ ∂ T ⎠ P ⎝ ∂ V ⎠T ⎝ ∂ T ⎠ P ⎝ ∂ T ⎠V
Interrelationship of CP and CV
⎛ ∂U ⎞
Putting the value of ⎜⎜ ⎟⎟ we get
⎝ ∂T ⎠P

⎛ ∂U ⎞ ⎛ ∂V ⎞ ⎛ ∂V ⎞ ⎛ ∂ V ⎞ ⎡⎛ ∂ U ⎞ ⎤
C P − CV = ⎜⎜ ⎟⎟ ⎜⎜ ⎟⎟ + P ⎜⎜ ⎟⎟ = ⎜⎜ ⎟⎟ ⎢⎜⎜ ⎟⎟ + P⎥
⎝ ∂ V ⎠T ⎝ ∂T ⎠P ⎝ ∂ T ⎠ P ⎝ ∂ T ⎠ P ⎢⎣⎝ ∂ V ⎠T ⎥⎦
For an ideal gas rate of change of U with V is zero at const T.

⎛ ∂V ⎞
C P − CV = ⎜⎜ ⎟⎟ P
⎝ ∂T ⎠P
For ideal gas RT
V =
P
So CP – CV = R
The interpretation of this equation is that, in a closed system of constant co
Interrelationship of C and C
any infinitesimal change in the internal energy is proportional to the in
changes of volume and temperature,Pthe coefficients of Vproportionality bei
Temperature, partial derivatives (Fig. 2.22).
dT T
In many cases
⎛ ∂V ⎞ ⎡partial
⎛ ∂U ⎞ derivatives
⎤ have a straightforward physical inte
dV CP and
− Cthermodynamics + P⎥
V =⎜ ⎟ ⎢⎜ gets ⎟ shapeless and difficult only when that interpreta
∂T
⎝ In⎠Pthe
kept in sight. ∂V
⎣⎝ present
⎠T case,
⎦ we have already met (∂U/∂T )V in eqn 2.15
saw that it is the constant-volume heat capacity, CV . The other coefficient,
plays a major role in thermodynamics because it is a measure of the v
The coefficient, (∂U/∂V)T, plays a major role in thermodynamics because it is a measure of the
verall change in U, which is the internal energyasofits
a substance as its volume is changed at constant te
variation of the internal energy of a substance volume is changed at constant temperature
arises when both V and T are (Fig. 2.23). We shall denote it π T and, because it has the same dimensions
ange. If second-order
but arises from the interactions between the molecules within the sample
are ignored, the overall We shall pressure:
denote it πT
internal
sum of changes for each
ately.
A ∂U D
πT = B E Definition of
C ∂V F T internal pressur

πT has
In the same
of dimensions
the notationasCpressure
terms V and πT, eqn 2.39 can now be written

πT arises from the interactionsdU = π T dV


between the+molecules
CV dT within the sample and hence it is called
πT
internal pressure
U
(b) The Joule experiment

When there are no interactions between the molecules, the internal ener
Joule - Thomson effect
When there are no interactions between the molecules, the internal energy is independent of
their separation and hence independent of the volume of the sample

For a perfect gas we can write πT = 0.

If the attractive forces between the particles dominate the repulsive forces, then the internal
energy increases (dU > 0) as the volume of the sample2.11increases
CHANGES (dV
IN>INTERNAL
0) and theENERGY
molecules 77
attract each other less strongly
ated. He then tried to measure the change in temperature of the water
en a stopcock was opened and the air expanded into a vacuum. He Repulsions
ange in temperature. πT > 0 dominant, π T < 0
ynamic implications of the experiment are as follows. No work was

Internal energy, U
If the
ansion into repulsive
a vacuum, so forces between
w = 0. No energythe particles
entered or leftdominate
the systemthe
at becauseattractive forces, then
the temperature the bath
of the internal
did energy decreases
not change, so q =(dU0. < 0) Perfect gas
within theasaccuracy
the volume
of theofexperiment,
the sample∆Uincreases
= 0. Joule(dV > 0) and
concluded theU
that
e when molecules
a gas expandsattract each other
isothermally strongly
and therefore that π T = 0. His
Attractions
wever, was crude. In particular, the heat capacity of the apparatus was
dominant, π T > 0
temperature change that gases do in fact cause was too small to mea-
πT < 0
ess, from his experiment Joule had extracted an essential limiting
as, a property of a perfect gas, without detecting the small deviations
Volume, V
real gases.
many useful properties and some that we shall draw on are dominant in a real gas, the internal
in Mathematical background 2. Skilful use of them can often
Joule - Thomson effect
energy increases with volume because the
uantity into a quantity that can be recognized, interpreted, or molecules become farther apart on average.
If repulsions are dominant, the internal
ose we want to find out how the internal energy varies with energy decreases as the gas expands.
James than
ressure rather Joulethe thought
volumethat
ofhe
thecould measure
system is kept πconstant.
T by observing the change in temperature of a gas
when
f eqn 2.41 (dUit =isπallowed to expand into a vacuum
T dV + CV dT) by dT and impose the con-
ure on the resulting differentials, so that dU/dT on the left
btain

Used two metal vessels immersed in a water


+ CV bath. One was filled with air at about 22 atm
and the other was evacuated
hermodynamics to inspect the output of a manipulation like
any recognizable physical quantity. The partial derivative on
on is theMeasured
slope of the
the plot of volume
change against of
in temperature temperature
the (at
property is normally
water tabulated
of the bath the expansion
when aasstopcock coefficient,
was opened
is defined
andasthe air expanded into a vacuum
High pressure Vacuum
gas
Definition of the
No work was done in the expansion
expansion into a [2.42]
coefficient vacuum, so w = 0
A schematic diagram of the
Fig. 2.25
So, whatever change in the internal energy should be observed as the
apparatus heat
used or theintemperature
by Joule an attempt to
tional change in volume
difference that
from the accompanies
first a rise in tempera-
law of thermodynamics measure the change in internal energy
means that the volume of the sample responds strongly to when a gas expands isothermally. The heat
Joule observed no change in temperature
. Table 2.9 lists some experimental values of α. For future absorbed by the gas is proportional to the
Joule - Thomson effect
No energy entered or left the system (the gas) as heat because the temperature of the bath did
not change, so q = 0.

Within the accuracy of the experiment, ∆U = 0 and Joule concluded that U does not change
when a gas expands isothermally and therefore that πT = 0

The heat capacity of the apparatus was so large that the temperature change that gases do in fact
cause was too small to measure

Later Joule and Thomson performed critical experiment in which an adiabatically contained
gas of volume V1 at pressure P1 was throttled through a porous diaphragm to the pressure P2
and the volume V2
Joule - Thomson effect
80 2 THE FIRST LAW

Thermocouples Porous Gas at U


barrier low pr
pressure
Let a gas expand through a porous barrier from one constant
pressure to another and monitored the difference of
temperature that arose from the expansion pi

The whole apparatus was insulated so that the process was


adiabatic.
pi

Here all changes to the gas occur adiabatically, q = 0


implies that ∆U = w.
pi
Insulation Gas at
high pressure

Joule and Thomson observed a lower temperature on the low pressure side, the difference in
Fig. 2.26 The apparatus used for measuring Fig
temperature being proportional to the pressure difference they maintained
the Joule–Thomson effect. The gas expands Jou
through the porous barrier, which acts rep
as a throttle, and the whole apparatus is gas
thermally insulated. As explained in the eit
text, this arrangement corresponds to an fro
THE FIRST LAW
Joule - Thomson effect
Thermocouples Porous Gas at Upstream Throttle Downstream
Here all changes to the gas occur adiabatically,
barrier q low
=0 pressure pressure
implies that ∆U = w. pressure

pi, Vi, Ti
pi pf
Now we need to find out the work done by the gas
to find out the change in internal energy

To calculate the work lets focus on the passage of a fixed


pi pf
amount of gas from the high pressure side, where the pressure
is Pi, the temperature Ti, and the gas occupies a volume Vi

The gas emerges on the low pressure side, where the same pf, Vf, Tf
pf
pi
amount of gas has a pressure Pf , a temperature
Insulation Gas atT , and
f
high pressure
occupies a volume Vf.

The apparatus used for measuring


Fig. 2.26 The thermodynamic basis of
Fig. 2.27
the Joule–Thomson effect. The gas expands Joule–Thomson expansion. The pistons
The pistons represent thethrough
upstream and barrier,
the porous downstream gases,
which acts which maintain
represent constant
the upstream pressures
and downstream
either side of the throttleas a throttle, and the whole apparatus is gases, which maintain constant pressures
thermally insulated. As explained in the either side of the throttle. The transition
THE FIRST LAW
Joule - Thomson effect
Thermocouples Porous Gas at Upstream Throttle Downstream
Lets say that the gas on the left is compressed
barrier isothermally
low pressure pressure
by the upstream gas acting as a piston pressure

pi, Vi, Ti
During this process the pressure is Pi and volume changes pi pf

from Vi to 0 2.12 THE JOULE–T


2.12 THE2.

So the isothermally
work done on by
the the
gas upstream
will be gas acting as a piston. The relevant pressure is pi and
isothermally
the volumeby isothermallyfrom Vby
the upstream
changes the
gas upstream
acting as gas acting The
a piston. as a piston.
relevant The relevantispressure
pressure pi and is pi and
i to 0; therefore, the work done on the gas is
the volume changes the volumefrom changes from Vi to 0;
Vi to 0; therefore, thetherefore,
work done the onwork thedone on the gas is
gas is
w1 = −pi(0 − Vi) = piVi pi pf
w1 = −pi(0 − Viw )= 1 =p−pVii(0 − Vi) = piVi

Enthalpy, H
i
The gas expands isothermally on the right of the barrier (but possibly at a different
The gasThe constant
gas expands
expands The
temperature)
isothermally gasonexpands
against
isothermally the right isothermally
theof
on pressure
the right
the onthe
pof the
f provided
barrier, right
by of
butbarrier the the barrier
downstream
(but possibly (but atpossibly
gas aact-
differentat a differen
ingconstant
at a different
constant constant
as temperature)
a piston temperature temperature)
to be driven out.the
against
against The
the against
volume the
changes
pressure
pressure pressure
from 0pby
pfPprovided f provided
to V
the
f the by
, sodownstream thedone
work downstream
gas act- gas act-
f
provided on the
ingbyasthe gas in
downstream
a piston ing
this as a
stage
to be driven piston
is
gas acting to be
out.asThe driven
a piston out.
volumeto be The
changesvolumefrom changes
0 to Vfrom , so 0 to
the V , so the work done
pfwork
, Vff, Tf done
f pf
driven on
outthe w on the gas in this stage
Gas is
at
pi
2 = −pf (Vf − 0) = −pfVf
gas in this stage is
Insulation
high pressure
w2 = −pf (Vf − 0) = −pfVf
wThe
2 = −p
totalf
work
(V f − done
0) = −ponfV the
f
gas is the sum of these two quantities, or
w = w + wThe
The total work done = ptotal
Fig. 2.26
i on
i the −work
V The V done
papparatus
f f gaseffect.
is the
onforthe
used gas is the sum
measuring Fig.of
2.27these two quantities,
The thermodynamic basisorof
1 2 Joule–Thomson
the Thesum of these two
gas expands quantities,expansion.
Joule–Thomson or The pistons
It follows that w change
through
the 1+
= wthe porous
of =barrier,
piVi −energy
w2internal pfVf acts
which of the gas asrepresent
it movesthe upstream andfrom
adiabatically downstream
w = w1 + w2 =aspaiV − p
throttle,
i V
fand f the whole apparatus is gases, which maintain constant pressures
one side of the barrier
Itthermally to the
followsinsulated. other
that theAschange is ofininternal
explained the energy
eitherofside
theofgas as it moves
the throttle. Pressure,
adiabatically
The transition from
= −p
w2 the f (Vf − 0) = −pfVf by the downstream gas act-

Enthal
constant temperature) against pressure pf provided
The total work done on the0 to
gas issothe sumdone
of these two quant
Joule - Thomson effect
ing as a piston to be driven out. The volume changes from
The total work done on the gas is the
on the gas in this stage is w = w + w = p V − p V
V , the work
f sum of these two quantities, or

w = w1 1+ w2 =2 piVii − ipfVf f f
w2 = −pf (Vf − 0) = −pfVf
It follows that the change of internal energy of the gas as it mo
The work
The total changedone on It
thefollows
of internal energy ofthat
gas is the the the
sumgas change
ofas twoofquantities,
it moves
these internal orenergy
adiabatically of the
from one side gas asbarrier
of the it moves
to adia
the other is oneside
one sideofofthethe barrier
barrier to the
to the other
other is is
w = w1 + w2 = piVi − pfVf
U −−UU= =ww
U
ff i i = p=Vp V
− p−Vp V
It follows that the change of internal energy ofi the
ii i f f f f
gas as it moves adiabatically from
one side of the barrier toReorganization
the other is
Reorganization of ofthis expression
this expressiongivesgives Pressure,
Reorganization of this expression gives p
Uf − Ui = w = piVi − pfVf U + p V = U + p V
fUf + pfVf = Ui + piVi or or Hf = H
f f i i i Hi
f = Hi
Reorganization of this expression
Therefore,gives
the expansion occurs without change of enthalpy.
Fig. 2.28 The iso
Uf + pfVf = Ui + piVi Therefore,
or Hf =the
Hi expansion occurs without change of enthalpy.
coefficient is the
respect to chang
Therefore, the expansion
The transition from theoccurs without
top diagram change
to the of diagram,
bottom enthalpy.which represents the passage temperature
of a bei
The property measured in the experiment is the
given amount of gas through the throttle, occurs without change of enthalpy ratio of the temperat
theThe
change property measured
of pressure, ∆T/∆p. inAdding
the experiment
the constraintis the ratio Porous
of enthal
of constant the te
He
he property measured the in
limitthe experiment
of small ∆p
the change of pressure, ∆T/∆p. Adding the constraint of constan
is the
impliesratio of
thatthe temperature
the change
thermodynamic to
quantity measure
plug
change of This
pressure, ∆T/∆p.
coolingwhich
by isenthalpic
Adding expansion is now called
the constraint the Joule–Thomson
ofcoefficient,
constant µ
enthalpy andeffect.
taking
the
imit of small ∆p implies
limitis
that
the
of
the
small ∆p
Joule–Thomson
thermodynamic
implies that
quantity
the . In other
thermodynamic
measured
words, the
is (∂T/∂p)Hto
physicalm
quantity
, the change in p
i
of µ is that
whichcoefficient, it is the ratio
is the Joule–Thomson of the change in temperature
µ. In other words, the p
ch is the Joule–Thomson µ. In other words, coefficient,
the physical interpretation
a gas expands under conditions that ensure there is no changeGas in enthal
of of
is that it is the ratio µTheis that
the changeit is the ratio
in temperature oftothe change
the change in temperature
in pressure
modern method of measuring µ is indirect, and involves m
when to flow
the cha
s expands under conditions that ensure there is no change in enthalpy.
w2 = −pf (Vf − 0) = −pfVf

Joule - Thomson effect


The total work done on the gas is the sum of these two quantities, or
w = w1 + w2 = piVi − pfVf
It follows that the change of internal energy of the gas as it moves adiabatically from
The property measured in the experiment
one sideis
of the ratio of
the barrier theother
to the temperature
is change to the change of
pressure, ∆T/∆p Uf − Ui = w = piVi − pfVf
Reorganization of this expression gives

f U +pV =U +pV
f f i i i for iH =H
Adding the constraint of constant enthalpy, implies that the thermodynamic quantity measured
Therefore, the expansion occurs without change of enthalpy.
is (∂T/∂p)H which is the Joule–Thomson coefficient, µ.

The property measured in the experiment is the ratio of the temperature change to
The physical interpretation of the
µ ischange
that itofispressure,
the ratio∆T/∆p.
of theAdding
changethein
constraint of constant
temperature to theenthalpy
changeand
intaking
the limit of small ∆p implies that the thermodynamic quantity measured is (∂T/∂p)H,
pressure when a gas expands under conditions that ensure there is no change in enthalpy
which is the Joule–Thomson coefficient, µ. In other words, the physical interpretation
of µ is that it is the ratio of the change in temperature to the change in pressure when
a gas expands under conditions that ensure there is no change in enthalpy.
The modern method of measuring µ is indirect, and involves measuring the isothermal Joule–
The modern method of measuring µ is indirect, and involves measuring the
Thomson coefficient, the quantity
isothermal Joule–Thomson coefficient, the quantity

A ∂H D
µT = B E Definition of the isothermal
[2.52]
C ∂p F T Joule–Thomson coefficient

which is the slope of a plot of enthalpy against pressure at constant temperature


(Fig. 2.28). Comparing eqns 2.51 and 2.52, we see that the two coefficients are related by
µ T = −Cp µ (2.53)
Reorganization of this expression gives

Joule - Thomson effect


Uf + pfVf = Ui + piVi or Hf = Hi
Therefore, the expansion occurs without change of enthalpy.

Since H is a state function H = f(P, T)


The property measured in the experiment is the ratio of the temperature cha
the change of pressure, ∆T/∆p. Adding the constraint of constant enthalpy and
⎛ ∂H ⎞ ⎛ ∂H ⎞
dH the
= ⎜ limit
⎟ dP + ⎜ ∆p
of small ⎟ implies
dT that the thermodynamic quantity measured is (∂T
⎝ ⎠ ⎝ ⎠
∂P isT the Joule–Thomson
which ∂T P coefficient, µ. In other words, the physical interpre
of µ is that it is the ratio of the change in temperature to the change in pressure
aCp ⎛ ∂H ⎞ under conditions that ensure there is no change in enthalpy.
gas=expands
⎜ ⎟
The⎝ ∂Tmodern
⎠P method of measuring µ is indirect, and involves measurin
isothermal Joule–Thomson coefficient, the quantity

At constant Enthalpy dH=0 A ∂H D


µT = B E Definition of the isothermal
C ∂p F T Joule–Thomson coefficient
⎛ ∂T ⎞ ⎛ ∂H ⎞
−C p ⎜ ⎟ = ⎜ ⎟
⎝ ∂P ⎠ ⎝ ∂P ⎠T
whichH is the slope of a plot of enthalpy against pressure at constant tempe
(Fig. 2.28). Comparing eqns 2.51 and 2.52, we see that the two coefficients are rela
µ T = −Cp µ
To measure µ T , the gas is pumped continuously at a steady pressure through
exchanger, which brings it to the required temperature, and then through a p
plug inside a thermally insulated container. The steep pressure drop is measur
the cooling effect is exactly offset by an electric heater placed immediately af
plug (Fig. 2.29). The energy provided by the heater is monitored. Because ∆H =
Joule - Thomson effect
Real gases have non-zero Joule–Thomson coefficients.

Depending on the identity of the gas, the pressure, the relative magnitudes of the attractive and
repulsive intermolecular forces, and the temperature, the sign of the coefficient may be either
positive or negative

A positive sign implies that dT is negative when dp is negative, in which case the gas cools on
expansion

Gases that show a heating effect (µ < 0) at one temperature show a82cooling effect
2 THE FIRST LAW (µ > 0) when
the temperature is below their upper inversion temperature, TI 600
Heating
Heatin

U
Nitrogen
µ>0 in

Temperature, T/K
400
For a given pressure, the temperature must be below a certain

Temperature, T
te
µ> 0
value if cooling is required but, if it becomes too low, the Cooling
Cooling µ<0 L
boundary is crossed again and heating occurs. 200 in
te
Hydro

Helium
0
Pressure, p 0 200
Pressure,
Fig. 2.30 The sign of the Joule–Thomson
coefficient, µ, depends on the conditions. Fig. 2.31 The inversion tempe
Joule - Thomson effect
For a perfect gas, µ = 0; hence, the temperature of a perfect gas is unchanged by Joule–
Thomson expansion.

Does this mean that we cannot cool/liquefy perfect gases?

When the perfect gas expands adiabatically then decrease in T should be expected because
expansion work is done but no heat enters the system

Implies internal energy falls, which in turn should reduce the temperature
Application of First law
to Thermodynamic Processes

•  With the help of the first law, one is able to calculate the
changes taking place in internal energy and enthalpy of
a system during a thermodynamic process.
•  Processes which are frequently studied and to which
this law will be applied include: i) Isothermal process ii)
Adiabatic process iii) polytropic processes.
•  In all these cases working substance of the system shall
be considered to be an ideal gas
Application of First law
to Thermodynamic Processes
i) Isothermal Process: The process is carried out when
dT = 0 thus dU = 0 . Hence
δq = δW = PdV
It is also true that in this case
Vf VfRT V f dV
q = w = ∫ PdV = ∫ dV = R T ∫
Vi Vi V Vi V
Vf ⎛Vf ⎞
= R T ∫ d ln V = R T ln ⎜⎜ ⎟⎟
⎝ Vi ⎠
Vi

If Vf > Vi i.e. for expansion of gas q is positive i.e. the system will
absorb heat from its surroundings and produce an equivalent amount
of work.
Application of First law
to Thermodynamic Processes
Application of First law
to Thermodynamic Processes
•  If Vf < Vi i.e. for compression of gas q is negative i.e. the system will impart heat to
the surroundings at the same time absorbing mechanical energy from them in the
form of mechanical work done on it.
•  The change in enthalpy of the system will be:

ΔH = H f − H i = ΔU + ( Pf V f − PiVi )
= R (T f − Ti ) = 0
Tf = Ti in the isothermal process.
•  Thus in an isothermal process with an ideal gas internal energy and enthalpy
remains unchanged and work done is equal to the heat exchanged.
Application of First law
to Thermodynamic Processes
ii) Adiabatic Process: There is no exchange of heat between the system and
surrounding i. e. δq = 0. Hence first law takes the form
dU = - δW = - P dV
Or dU = CV dT = - P dV
This indicate that system will perform work at the cost
of its internal energy and therefore the lowering of
temperature of the system will result. Tf
Adiabatic work done (w)
= − CV ∫ dT = − CV (T f − Ti )
Ti

Change in Internal energy = CV (Tf – Ti)


Adiabatic Process

Relationship between P and V and T and V in


adiabatic process.
dV
CV dT = − R T
V
Or
CV dT dV
=−
R T V
Integration of this equation under the limiting
condition
V = Vi at T = Ti
And
V = Vf at T = Tf
Adiabatic Process

And substituting the expression for R in above


Expression CV Tf Vf
ln = − ln
C P − CV Ti Vi

Or T f V f γ −1 = Ti Vi γ −1 where CP
γ =
CV
Or TV γ −1
= Const Or
PV γ = Const

Also since by definition H = U + P V


Or dH = dU + P dV + V dP
As dU = - P dV
So dH = V dP
Adiabatic Process

Enthalpy change in a adiabatic process is


Pf Vf
ΔH = ∫ V dP = − γ ∫ P dV
Pi Vi

As PV γ = Const for such process.


This on integration lead to the expression
γ −1
γ Pi Vi ⎡⎢⎛⎜ Vi ⎞ ⎤
ΔH = ⎟ − 1⎥
γ −1 ⎢⎜⎝ V f ⎟
⎠ ⎥
⎣ ⎦
Adiabatic Process

Work done in reversible adiabatic expansion can


be deduced as follows
V2 V2 dV
w= ∫ PdV = m ∫
V1 V1 Vγ
⎛ V21− γ − V11− γ ⎞
= m⎜⎜ ⎟⎟
⎝ 1 −γ ⎠
Or
P2V2 − P1V1
w=
1− γ
Where

P V γ = m = a const.
Polytropic Process

iii) Polytropic process: The general expression for this process is


n
PV = const.
The work done in this process is similar to adiabatic process but
γ ≠n
PiVi − Pf V f
w=
n −1
n −1
PiVi ⎡⎢⎛⎜ Vi ⎞ ⎤
=− ⎟ −1⎥
n − 1 ⎢⎜⎝ V f ⎟
⎠ ⎥
⎣ ⎦
Polytropic Process

Change in Internal energy = CV (Tf – Ti)


Internal energy can also be expressed in terms of P and V as follows:
Tf
ΔU = − CV ∫ dT = − CV (T f − Ti )
Ti

⎛ Pf V f PV ⎞ C P V ⎡ Pf V f ⎤
= CV ⎜⎜ − i i ⎟⎟ = V i i ⎢ − 1⎥
⎝ R R ⎠ R ⎣ PiVi ⎦
n −1

CV Pi Vi ⎢⎜ V i ⎟
⎛ ⎞ ⎤
= − 1⎥

R ⎢⎝ V f ⎠ ⎟ ⎥
⎣ ⎦
From the first law heat exchanged q is obtained as
n −1
[CV (n − 1) − R] Pi Vi ⎡⎛ V ⎞ ⎤
q= ⎢⎜ i ⎟ −1⎥
R (n +1) ⎢⎜⎝ V f ⎟
⎠ ⎥
⎣ ⎦

For n = γ; q = 0 obtained from the above expression which is true for adiabatic
process.
Polytropic Process

Change in enthalpy of the system is given by


ΔH = ΔU + (Pf V f − Pi Vi )
Substituting the expression for ΔU in above expression

n −1
[CV + R] Pi Vi ⎡⎛⎜ Vi ⎞ ⎤
ΔH = ⎢ ⎟ −1⎥
R ⎢⎜⎝ V f ⎟
⎠ ⎥
⎣ ⎦
Or
n −1
C P Pi Vi ⎡⎛⎜ Vi ⎞ ⎤
ΔH = ⎢ ⎟ −1⎥
R ⎢⎜⎝ V f ⎟
⎠ ⎥
⎣ ⎦

Above equation show that for n = 1 i.e. isothermal process with ideal gas , both
change in internal energy and enthalpy are equal to zero.
Summary of Thermodynamic
Processes
Process characteristics P-V-T Work done Heat exchange
relationship
Isothermal dT = 0 PV = const RT ln (Vf / Vi) RT ln (Vf / Vi)
Isochoric dV = 0 P/T = const 0 Cv (Tf – Ti)
Isobaric dP = 0 V/T = const Pi(Vf – Vi) Cp (Tf – Ti) +
Pi(Vf – Vi)
Adiabatic q=0 PVγ = const (PfVf - Pi Vi) / (1- γ) 0
polytropic - PVn = Const (PfVf - Pi Vi) / (1- n) Cv (Tf – Ti).
(γ - n)/(1-n)
MM209 - Thermodynamics
Instructor : Aswani Yella
⎛ INTRODUCTION
∂ G′ ⎞the distinction
o156introduced ∂S′THE
⎛ TO between
⎛ CP ⎞ the heat
⎞ THERMODYNAMICS capacity per
OF MATERIALS, SIXTHmole
EDITION
⎜ ⎟ = −⎜ ⎟ = −⎜ ⎟ (5.12)
e heat capacity
∂T 2 of the⎝ ∂entire
T ⎠ substance
⎝ T ⎠ as follows:

Variation ⎠P of heat P
Capacity with Temperature
in which c p and c v are, respectively, the constant-pressure and constant-volume
thatCheat
nmolar the = ncv dTand
v dTfollowing
capacities theorinternal
holds for dU = cv and
theenergy dT enthalpy areheat
constant-volume (2.6a)
givencapacity:
for 1 mole of the
substance. Integration of Equation 2.6b between the states (T 2 ,P ) and (T 1 ,P ) gives
C dT2 = between
the difference
p⎛ nc dT the molar
∂ A′ ⎞ p ⎛ ∂S′ ⎞
dH = c ofdTthe two states as
or enthalpies (2.6b)
⎛ CV ⎞p
⎜ 2 ⎟ = −⎜ ⎟ = −⎜ ⎟ T2
⎝ ∂T ⎠V ∂T T
⎝∆H = ⎠HV(T2 , P )⎝− H (T⎠1, P ) = ∫T1
c p dT (6.1)

so introduced
from which it isthe
Knowledge ofdistinction
seen the between
thatvariation
knowledgeof of the
cp the
with heat capacity
temperature
variation per mole
is required
of c p with 155
for the
temperature is
erequired
heatdetermination
capacity
for the of the
of entire substance
the temperature
determination of as follows:
dependence
the temperature of the enthalpy.
dependence of the enthalpy.
Similarly, integration of Equation 2.6a between T 2 and T 1 at constant volume shows
Cv dT = nc
that knowledge of the
v dT
variation
or of cdU = ctemperature
v with
v dT
is required for the determina-
(2.6a)
tion of the temperature dependence of the internal energy. Later in this chapter, we
will show that this is also the case for the determination of the temperature depen-
Cofp dT
denceIntegration
= nc pof
entropy. Thus,
or dH
dTdUbybetween T2 =
knowing the andc pT
dT1 at constant
temperature volume
dependence
(2.6b)
shows
at constant that
pressure
knowledge
(volume) ofcapacity
of the heat the variation of cv with
as a function temperature
of temperature, weiswill
required
know theforGibbs
the
determination
(Helmholtz) of change
free energy the temperature dependence
with temperature, of the
which will internal
enable energy.
us to determine
the equilibrium state of the system in question.
155
Variation of heat Capacity with Temperature
In 1819, as a result of experimental measurements, Dulong and Petit
introduced an empirical rule which states that the molar heat capacities
(cv) of all solid elements have the value 3R

Although the molar heat capacities of most elements at room temperature


have values which are close to 3R, subsequent experimental measurement
showed that the heat capacity usually increases slightly with increasing
temperature and can have values significantly lower values than 3R at low
temperatures
Variation of heat Capacity with Temperature
HEAT CAPACITY, ENTHALPY, ENTROPY 157

25

20 Pb

cv, joules/mole.K 15 Cu

10 Si

5
Diamond

0
0 50 100 150 200 250 300
Temperature, K

Although leadFigure
and 6.1 The constant-volume molar heat capacities of Pb, Cu, Si, and diamond as func-
copper closely
tions of obey Dulong and Petit’s rule at room temperature, the constant
temperature.
volume heat capacities of silicon and diamond are significantly less than 3R at room temperature
each of the 3n oscillators is not influenced by the behavior of its neighbors, and
assigned a single frequency ν to each of the oscillators. Such a system of quantum
oscillators is now called an Einstein solid (sometimes an Einstein crystal ).
For a fixed frequency of vibration, the energy levels of a quantum harmonic
Notice the significant decrease in the heat capacities at low temperatures.
oscillator take values of the i th energy level as
(1 − exp( ))
kT

exp(
)
Variation of heat Capacity with Temperature
2
9nh 3 vD 2 ⎛ hν ⎞

which, with x = hν/ckv B=
T , gives
k BθD 0
2 3
v ⎜ ⎟
kT
⎝ k BT ⎠ (1 − exp( ))2h ν
dv

3 θ T kT
Calculation of the heat capacity⎛ofT a⎞solid D element,
4 − x as a function of temperature, was one of
xe
c = 9 R ⎜ ⎟
the early successful applications⎝ θofD quantum
which, with x = hν/k BT , gives
v
⎠ 0 ∫
(1theory
dx
− e ) to the solid state
− x 2
(6.7)

where:
3
⎛ T ⎞ θD T x 4 e − x
v D (the Debye frequency) = v max
cv = 9 R ⎜ Debye
θD = hν D /k B is the characteristic
θ ⎟
⎝ D ⎠ ∫
temperature dx
− x 2of the solid
(1 − e ) 0
(6.7)

Equation 6.7 is compared with Einstein’ s equation in Figure 6.2b. Debye’ s equation
where:approaches thexDulong = hν/kBandT Petit limit at high temperatures and shows an excellent
θD = hνdata
D /kBat
islower
the characteristic Debye temperature of the solid
vfitD to theDebye
(the experimental
frequency) = v max temperatures. Figure 6.3 shows the curve fitting
of Debye’ νD is the
s/kequation to Debye
the frequency
measured heat capacities of Pb,ofAg, Al, and diamond.
θ D = h ν D B is the characteristic Debye temperature the solid
The curves are nearly identical, except for a horizontal displacement. The relative
horizontal displacement is a measure of θ D . When plotted as c v versus log T /θD, the
Debye’s
Equation equation approaches the Dulong and Petit limit at high temperatures and shows an
data in 6.7Figureis compared
6.3 fall on with Einstein’
a single s equation
curve. This in Figure
is an example of a6.2b.
law ofDebye’ s equation
correspond-
excellent fit
approaches to the experimental data
limitatat
lower temperatures
ing states.the WeDulong and Petit
will see another example highwhen
of this temperatures
we study the and
vanshows an excellent
der Waals gas
fit tointhe experimental
Chapter 8. data at lower temperatures. Figure 6.3 shows the curve fitting
of Debye’
TheThe svalue
value equation
of of
thethe to the in
integral
integral measured
in Equation
above heat
6.7 capacities
equation from
fromzero
zerotoof Pb,
infinity
to Ag, isAl,
is 25.98,
infinity and diamond.
andand
25.98, thus,thus, for very low
Thefor very low
curves
temperatures, aretemperatures,
nearly Equation
above identical,
equation 6.7 becomes
except
becomes for a horizontal displacement. The relative
horizontal displacement is a measure of θ D . When plotted as c v versus log T /θD, the
3 3
data in Figure 6.3 fall onc a =single ⎛ ⎞ ⎛ ⎞
curve. This is an example of a law of correspond-
T T
v 9 R × 25.98 ⎜ ⎟ = 1944 ⎜ ⎟
ing states. We will see another example⎝ of ⎠ when⎝ we
θ D this θ D ⎠study the van der Waals gas
e 6.3 fallFigure
on a single
6.2bcurve. This is an example
(b) Comparisons of theof a law heat
Debye of correspond-
capacity,0the Einstein heat capacity, and the
0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0
actual
e will see another example heat
of this capacity
when of aluminum.
we study the van der Waals gas
Variation of heat Capacity with Temperature
T/q
(b)

30
of the integral in Equation 6.7 from zero to infinity is 25.98, and thus,
Figure 6.2b (b) Comparisons of the Debye heat capacity, the Einstein heat capacity, and the
emperatures, Equation 6.7 becomes actual heat capacity of aluminum.
25
30
3 3
⎛ T ⎞ Pb ⎛ T ⎞
cv = 9 R × 25.9820⎜ ⎟ = 1944
cv, joules/K.mole ⎜⎝ θ ⎟⎠
25
⎝ θ D ⎠ qD = 90.3 D Pb

cv, joules/K.mole
20
qD = 90.3
15
Ag 15 Ag
ed the Debye T law for low-temperature heat
3 capacities.
qD = 213 Al qD = 213 Al
3
theory Debye’s
does notTconsider
law for lowcontribution
10 the temperature made
heat capacities
to the heatqDcapac-
= 385
10 qD = 385
Diamond
take of energy by free electrons at the Fermi level in a metal at5 low
Diamond qD = 1890
5 0 qD = 1890
al at low temperatures, the heat capacity varies as 1.0 2.0 3.0
log10T
0
1.0 2.0 3.0
Debye’s theory does not consider the contribution
Figure 6.3made to the heatmolar
The constant-volume capacity by the
heat capacities uptake
of several of
solid elements. The curves
log10Tare the Debye equation with the indicated values of θD .
energy by free electrons at the Fermi level in a metal at low
temperatures ⎛ T ⎞
cv = γT + 1943 ⎜
3

⎝ θD ⎟⎠
Figure 6.3 The constant-volume molar heat capacities of several solid elements. The curves
are theFor
Debye equation
a metal at lowwith
Thus, at temperatures
the indicated
temperatures, the values of θ D . varies
approaching
heat capacity
0 K, c v for a metal varies linearly with T .
as
Because of the various uncertainties in the theoretical calculation of heat capaci
ties, it is normal practice
3
to measure the variation of the constant-pressure molar hea
capacity with⎛ Ttemperature
⎞ and express the relationship analytically.
cv = γT + 1943 ⎜ ⎟
⎝ θD ⎠
Thus, atattemperatures
Thus, temperaturesapproaching 0 K,0cvK,
approaching forcav metal varies linearly
for a metal with T. with T .
varies linearly
Variation of heat Capacity with Temperature
•  Experimental data consists of CP as function of temperature.
•  For the liquid and solid, The P V term is very small. Hence H
is taken as equal to U and CP as equal to CV.
•  In other words no distinction is made between CP and CV so
far as applications are concerned.
•  It has been found that experimental CP Vs. T data for elements
and compounds fit best with an equation of type:
CP = a + b T + c T-2
Variation of heat Capacity with Temperature

•  Where a, b, c are empirically fitted constant and


differ from substance to substance.
•  The last term is the smallest and therefore often
ignored.
•  In some cases, such as liquid metals, both bT and
cT-2 are usually ignored.
•  The above expression is also valid for diatomic
and polyatomic gases as well.
The experimentally
experimentally measuredmeasured
variation variation of the constant-pressure
of the constant-pressure molar heat molar he
acity Variation
The experimentally
of a material
of a material of
with temperature
with heat
measured
temperatureCapacity
variation
is normally
is normally anwith
oftothe
fitted Temperature
constant-pressure
expression
fitted to an molar heat
ofexpression
the form of the for
capacity of a material with temperature is normally fitted to an expression of the form
c
c p = a + bT + cc
ccpp ==Ta ++bT
2
bT++ 2 2
TT
be It
noted
Thisthat
should bethe
expression analytical
noted isthat
onlythe expression
applicable is only
in theexpression
analytical stated applicable
temperature
is onlyrange inover
thewhich
applicable stated thetem-
in the values of
stated tem-the
hould
range be
heat
over
perature noted
rangethat
capacity
which thethe
were
over values
whichanalytical
measured andthe
of
the
fit to
values expression
heatthe equation
of capacity is only
were
the heat capacity applicable
measured
were and fit
measured inand
thefitstated
to to tem
ature
tion.therange
For over
example,
equation. Forwhich
ZrO theZrO
2 exists
example, values ofasthe
as2 monoclinic
exists α -ZrOcapacity
heat
monoclinic 2 from
α -ZrOroom weretempera-
measured and fit
2 from room tempera-
478 K and
equation.
ture as
For
to 1478 tetragonal
Kexample, β -ZrO
ZrO
and as tetragonal βthe
2 2inexists
-ZrO range
2as of range
temperature
in monoclinic
the α 1478–
-ZrO
of temperature 2670
from
1478– K,room
2670 K,temper
Eg: ZrO 2 exists as monoclinic α-ZrO 2 from room temperature to 1478 K and
2 as tetragonal β-
polymorph
to and
1478 each
ZrO 2K
has its
andrange
the asown
in polymorph hasequation
its own
tetragonal
of temperature βgiving
equation
-ZrO
1478–2670 the
in
K, variation
giving
the
and the
range
each ofofitstemperature
variation
polymorph heat
has capacity
ofitsits
own heat capacity
1478– 2670 K
equation
2
with
perature. temperature.
giving the variation of its heat capacity with temperature.
each polymorph has its own equation giving the variation of its heat capaci
h temperature.α − ZrO 2 c = 69.62 −37.53 × 10 −3 T − 14
+ 2 × 10 5 T −2 J/K ⋅ mole
5 .0−6
α − ZrO c = 69.62 + 7.53 × 10 T − 14.06 × 10 T J/K ⋅ mole
p
2 p
over the temperature range 298–1478 K
over the temperature range 298– 1478 K, and
α −range
temperature c p =1478
ZrO2298– 7.53 × 10 T − 14.06 × 105 T −2 J/K ⋅ mole
K, +and
69.62 −3

β − ZrO2c p = 74.48 J/K ⋅ mole


r the temperatureβ range
− ZrO2c p = 74.48 J/K ⋅ mole
298– 1478 K, and from 1478 to 2670 K
from 1478 to 2670 K. At the transition temperature, the heat capacity drops by about
8 to5.6
2670
At
J/K⋅ K.
the At the
transition
mole. transition
temperature,
In fitting the temperature, the
the heat capacity
analytical heat
drops
expression to capacity
bythe
about drops
5.6 J/K
measured by
mole.
heat about a , b ,
capacities
mole.and
In cfitting the analytical
β expression
− ZrO2c p to = 74
the
.48 J/K ⋅ mole
measured heat capacities a , b ,
, each have nonzero values in the expression for α -ZrO 2 , whereas the molar heat
Variation of heat Capacity with Temperature
HEAT CAPACITY, ENTHALPY, ENTROPY 163

140

Si3N4 Al2O3

120

100

MoSi2

cp, joules/mole.K
80

60 AlN

Cu(l)
40 O2

20 Cu
C(graphite)
C(diamond)
0
300 500 700 900 1100 1300 1500
Temperature, K

The variations, with temperature,


and compounds. of the constant-pressure heat
Figure 6.4 The variations, with temperature, of the constant-pressure heat capacities of sev-
eral elements

capacities of several140elements and compounds.


b-CaF2
120

CaF2(l)
100 a-CaF2
a-CaC
0
300 500 700 900 1100 1300 1500
Temperature, K

Variation of heat Capacity with Temperature


Figure 6.4 The variations, with temperature, of the constant-pressure heat capacities of sev-
eral elements and compounds.

140
b-CaF2
120

CaF2(l)
100 a-CaF2
a-CaC2
cp, joules/mole

a-ZrO2
80
b-CaC2 b-ZrO2

60
g-Mn d-Fe
d-Mn
a-Fe
40
a-Mn g-Fe Fe(l)
b-Mn Mn(l)
20

0
300 500 700 900 1100 1300 1500 1700 1900
Temperature, K

The variations,
Figure 6.5 Thewith temperature,
variations, ofconstant-pressure
with temperature, of the the constant-pressure
molar heat capacities
of some elements which exhibit allotropy and some compounds which exhibit
molar heat
capacities of some elements which exhibit allotropy and some
polymorphism.

compounds which exhibit polymorphism.


Variation of heat Capacity with Temperature
If specific heat values of compounds are not known from
experimentation, it can be approximately evaluated by the use of 'Kopp
Rule’ suggested in 1864.

The specific heat of a compound Ax.By shall approximately be given by


a formula as : Molar Sp. Heat of Ax.By= x.sp.heat of A + y.sp. heat of B
per g atom

This is fairly reliable for ionic compounds wherein the individual


elements obey Dulong and Petit's law.

This is extended to solutions, metallic as well as non- metallic, to work


out approximate values of specific heats from the specific heat values of
individual components.
The specific heat of solutions is equal to the weighted sum of the
heat capacities of the components.
Variation of Enthalpy with Temperature

•  Change in enthalpy during the course of process (ΔH) is


equal to the heat supplied to the system (q) at constant
pressure.
•  The constant pressure restriction is mostly not important
for example H is not function of P for ideal gases.
•  Energies of solid and liquids are hardly affected by some
changes in pressure due to their very small molar
volumes. In other words, the VdP term is negligible.
•  In most metallurgical and materials processing, gases are
ideal and pressure is maximum a few atmosphere.
Therefore ΔH = q approximation is quite all right.
Thermochemistry
•  It may be defined as the branch of science which deals with the study of
heat exchanges associated either with chemical reaction or physical
changes in the state of matter such as melting, sublimation or evaporation
etc.

•  If heat is produced by a chemical reaction it is denoted by – ve sign


(Exothermic reaction)
•  The release of heat signifies a decrease in the enthalpy of a system, we can
now see that an exothermic process is one for which ∆H < 0
•  If heat is absorbed during a chemical reaction it is denoted by +ve sign
(endothermic reaction).
•  Because the absorption of heat results in an increase in enthalpy, an
endothermic process has ∆H > 0

•  exothermic process: ∆H < 0 endothermic process: ∆H > 0


Thermochemistry
Changes in enthalpy are normally reported for processes taking place
under a set of standard conditions.

we shall consider the standard enthalpy change, ∆H, the change in


enthalpy for a process in which the initial and final substances are in
their standard states:

The standard state of a substance at a specified temperature


is its pure form at 1 bar.
Eg: the standard state of liquid ethanol at 298 K is pure liquid ethanol at
298 K and 1 bar; the standard state of solid iron at 500 K is pure iron at
500 K and 1 bar

The standard enthalpy change for a reaction or a physical process is the


difference between the products in their standard states and the reactants
in their standard states, all at the same specified temperature
That is, the solidification of liquid A , whose equilibrium solidification temperature
Thermochemistry
(which is also the equilibrium melting temperature) is T 2 . The segment cd is the
change in enthalpy at the equilibrium liquid-to-solid transformation; that is, it is
the heat of solidification and can be seen to be H S (T 2 ) – H L (T 2 ) < 0 (exothermic). A
Absolutesupercooled
value of enthalpy change
liquid can of atosubstance
transform a solid at is
T 1not
. Theknown. Only weofcan
molar enthalpy measure are
transforma-
changestion at this temperature can be determined, since the enthalpy is a state function.
of enthalpy.
Thus,

The changes in enthalpy (caused)by changes


( in) temperature
( ) and/or( composition
)
∆H b → a = ∆H b → c + ∆H c → d + ∆H d → a (i)
can be
graphically represented on an enthalpy–temperature diagram

HL (T2) c
Liquid
b
HL (T1)
Enthalpy

HS (T2) d

d
Soli

HS (T1) a

T1 T2

Figure 6.6 The variation, with temperature, of the molar enthalpies of the solid and liquid
phases of a substance.
Classification of Enthalpy change
•  Enthalpy change occur due to various causes.
•  Sensible heat: enthalpy change due to change of
temperature of a substance is known as sensible heat. It
is divided into:
•  Enthalpy change due to changes in state of aggregation
of substance
•  Enthalpy change without any change in aggregation of
the substance
•  Heat of reaction
•  Heat of mixing
Classification of Enthalpy change
i) Enthalpy change due to changes in state of aggregation of
substance : These are isothermal processes. By convention
enthalpy changes for all isothermal processes are
designated by ΔH. For example,
ΔHm = enthalpy change of one mole of solid due to melting
(i. e. latent heat of fusion per mole )
ΔHv = enthalpy change of one mole of liquid due to
vaporization (i. e. latent heat of vaporization per mole )
Classification of Enthalpy change
Consider a pure substance A, which is undergoing
following changes during heating from 298 to T K

A (Solid) → A (Liquid) → A (Gas) → A (Gas)


at 298 K at Tm at Tb at T
Tm and Tb are the melting and boiling points of A.Then
Tm Tb
H T − H 298 = ∫ CP ( s) dT + ΔH m + ∫ CP (l ) dT
298 Tm
Tm
+ ΔHV + ∫ CP ( g ) dT
Tb

Cp (s), Cp (l) and Cp (g), are for solid liquid and


gaseous A. it is only applicable for pure substance.
Classification of Enthalpy change

ii) change in enthalpy without any change in


aggregation of the substance:
As a universal convention, thermo chemical data
books take sensible heat at 298 K (250C) as zero for
any substance. Hence sensible heat at temperature T,
per mole of a substance is given as:
T
H T − H 298 = ∫ CP dT
298

298 K is known as reference temperature


Classification of Enthalpy change
Putting the expression for heat capacity, we get

T
∫ (a + b T + c T )dT
−2
H T − H 298 =
298

= a (T − 298) + b
2
(T 2 2
)
− 298 − c (T1 − 1
298
)
2 −1
= AT + B T − C T + D
Where A, B, C and D are lumped parameters and functions
of empirical constants a, b, c
Classification of Enthalpy change
Heat of mixing (ΔHmix): This is the change of enthalpy that
occurs when a substance is dissolved in solvent.
This process is generalized as
A (pure) = A (in solution)
This process is also accompanied by a change of enthalpy
(ΔHmix), where
(ΔHmix) = HA (in solution) – HA (pure)

Again by convention, the process is assumed to be isothermal


for thermodynamic calculations
Classification of Enthalpy change
Heat of reaction (ΔH): This is the change of enthalpy that occurs
when a reaction takes place. By convention reaction is considered to
be isothermal. Consider the following reaction occurs at
temperature T:
A (pure) + BC (pure) = AB (pure) + C (pure)
Then
ΔH (at T) = ΔHAB (at T) + ΔHC (at T) - ΔHA (at T) - ΔHBC (at T)

Where ΔHAB , ΔHBC, ΔHA and ΔHc are molar enthalpies


of pure AB, BC, A and C, respectively.
Some comments:
•  For calculation of enthalpy change, reactions, dissolutions
and phase transformations has been assumed to occur
isothermally. Since enthalpy is a state property, it depends
only on initial and final states and not the path.
•  For a reversible isothermal process, the temperature
remains constant all through. If the process is not
reversible, then temperature at the beginning and end of a
process would be same. In between, temperature can vary
significantly.
Hess s Law

It states that the total heat exchanged in a given chemical reaction, which may take place under
constant pressure, volume or temperature is the same irrespective of the fact whether it is
made to take place over a path involving formation of number of intermediate products or
over the one involving the formation of final product from the reactant directly in one stage.

ΔH =ΔH1+ΔH2+ΔHx+ΔHy

The total heat exchanged in a chemical process is the same irrespective of whether the process
occurs in a direct single stage or through multiple stages.
Hess s Law
Eg: Reduction of iron oxide by carbon or carbon-monoxide gas
The reaction can be carried out in one stage as
Fe2O3 + 3C = 2Fe + 3CO

ΔHrxn = 2HFe + 3HCO – 3HC – HFe2O3

The same reaction can be carried out in multiple stages as


3Fe2O3 + C = 2Fe3O4 + CO
2Fe3O4 + 2C = 6FeO + 2CO
6FeO + 6C = 6Fe + 6CO
thus:
The enthalpy change in reaction (2.4i]) i.e. single stage is gi\,€n by

AH1z.+s1 = 2HreHessQ'a b
and enthalpy change in reactions
s
+ 3Hco - 3Hc- Law
l
Hr".o.
(2.46) are
(2An

(2.48)
= 2HFeooq + Hco - 3H5er9. - H6
AH1z.aal
IHp.+sy - 6Hneo + 2Hco - 2Hresg. - 2Hc (2.4e1

Calculate theAHlz.my=
enthalpy 6Hreof+ formation
6l-lco - 6Hreo of WC from the following(2.50)
- 6Hc
which on addition gives the same equation as inEq. Q'al
data at 25 C
Example : Calculate the enthalpy of forrnation of WC from the follcnrving data at 25 C:

(1) wC + z| oz - Wos + Coz

AHo = -285800 caVg mole


(21 C+ Oa=COz
AHo = -940950 cali g mole
(3) w +'tloz - 'z
wos
AHo = -195700cailgmole
Solution : WC is formed from C and Was
W+ C- WC
and is obtained by addition of equations 2 and 3 and subtracting from this, equation 1
and

the algebric summation of the AHo values give the required enthalpy change as
AHo= AHz+693 -AHr
(-285800)
: -;ff' ;r]ffl"*
2.10 HEAT CAPACITY CALCULATIONS

Heat capacity for any substance is not a fixed value. For the same material it changes
with temperature and the way it changes with temperature varies considerably from
sub-
relationship has to be established experimentally. Howewl
Kirchoff s Law
Utility:

It allows us to calculate the enthalpy changes at


various temperatures, provided the enthalpy is
known at some other temperature, and the heat
capacity of the reactants and products are known in
the range of temperatures under consideration.
Derivation:

Consider a chemical reaction at temperature T1


whose enthalpy change is ΔH1. Calculate the
enthalpy change ΔH2 at temperature T2.
Kirchoff s Law
The product of this reaction at T2 can be obtained in many
different ways. Let us, however, consider the reaction to be
carried out first by reacting the reactants (x+y) at T1 and then
raising the temperature of the products from T1 to T2 along
ABC.
Kirchoff s Law
The heat absorbed by this process will be
T2
ΔH1 + ∫ CPz dT
T1

The second way of obtaining the same result is to


raise the temperature of the reactants from T1 to
T2 and then react them together at T2 i. e. along
ADC. The heat absorbed by this process is
T2

ΔH 2 +
∫ (C
T1
Px )
+ C P + dT
y
Kirchoff s Law
According to Hess s law the heats absorbed during the two ways of
producing z must be the same since the initial conditions of the reactants
and final conditions of the products are in each case the same.
T2 T2
ΔH 2 +
∫ (C Px )
+ C P + dT
y
= ΔH1 + ∫ T1
CPz dT
T1

Or ΔH 2 − ΔH 1 = ∫
T2

T1
[C − (C
Pz Px + C Py dT )]
Or T2
ΔH 2 − ΔH 1 = ∫ Δ C P dT
T1

Or T2
ΔH 2 = ΔH 1 + ∫ Δ C P dT
T1
Kirchoff s Law
Since all the terms are known in the right hand of
the equation, ΔH2 can be calculated. We know
T2
ΔH 2 − ΔH 1 = ∫ Δ C P dT
T1

This is the statement of the Kirchoff s law.


It means the rate of change of enthalpy of a process
or a reaction with temperature is given by the
difference of the heat capacity at constant
pressure of products and reactants taking part in
the reaction ⎛ ∂ ΔH ⎞
⎜⎜ ⎟⎟ = Δ C P
⎝ ∂T ⎠P
Thermochemistry
166 166 INTRODUCTION TO THE
INTRODUCTION THERMODYNAMICS
TO THE OF OF
THERMODYNAMICS MATERIALS, SIXTH
MATERIALS, EDITION
SIXTH EDITION
Convention assigns the value of zero to the enthalpy of elements in
their stable states at 298 K (25°C) and P = 1 atm.
of oneofmole
one mole
of theofcompound
the compound
fromfrom its elements
its elements at 298
at 298 K and
K and P =P1=atm.
1 atm.
ForFor example,
example,
for theforoxidation
the oxidation reaction
reaction
For example, for the oxidation reaction
1) + 1
M(+solid O2( gas) = MO(solid ) at 298 K and P = 1 atm
M(solid ) O ( gas ) = MO( solid ) at 298 K and P = 1 atm
22
2
1
∆H 298 = H MO(s )298 − H M( s )2981−
∆H 298 = H MO(s )298 − H M( s )298 − H2O2H( gO)298
2 ( g ) 298

2
and, since H M,298 and H O2 ,298 are by convention set equal to zero, then
and, since HSince
M,298 and are H
H O2 ,298and
HM,298 by convention set equal to zero, then
O2 ,298 are by convention set equal to zero
∆H 298 = H MO,298
∆H 298 = H MO,298
The variation of heats of chemical reaction (or heats of formation) with temperature
The variation of pressure
at constant heats of chemical reaction (or
can be represented on heats of formation)
an enthalpy– with temperature
temperature diagram, such
at constant pressure
as those can6.7a
in Figure be and
represented on an
b, which are enthalpy–
drawn for thetemperature diagram, such
oxidation reaction
as those in Figure 6.7a and b, which are drawn for the oxidation reaction
1
Pb + O2 = PbO
1
Pb + O22 = PbO
2
The pertinent thermochemical data for this system are listed in Table 6.1.
∆H 298 = H MO,298

Thermochemistry
Figure 6.7b (b) The variation, with temperature, of the enthalpies of (Pb + 1/2O 2 ) and PbO.
The variation of heats of chemical reaction (or heats of formation) with tem
at constant pressure can be represented on an enthalpy– temperature diagr
Table 6.1 Thermochemical Data for Pb, PbO, and O2 as those in Figure 6.7a and b, which are drawn for the oxidation reaction
HPbo(298) = –219,000 J/K
1
Pb + O2 = PbO
The variation of heats of chemical reaction (or heats of formation) with
cp,Pb(s) = 23.6 + 9.75 × 10–3T J/K from 298 K to Tm,Pb
cp,Pb(l ) = 32.4 – 3.1 × 10–3T J/K from Tm,Pb to 1200 K
2

temperature at constant pressure can be represented on an enthalpy–


cp,PbO(s) = 37.9 + 26.8 × 10–3T J/K from 298 K to Tm,Pbo The pertinent thermochemical data for this system are listed in Table 6.1.
cp,O2(g) = 29.96 + 4.18 × 10–3T – 1.67 × 105T–2 J/K from 298 K to 3000 K In Figure 6.7a:
temperature diagram
∆Hm,Pb = 4810 J at Tm,Pb = 600 K
Tm,PbO = 1159 K
50

40
• a represents the enthalpy of 1/2 mole of oxygen gas and 1 mole of Pb( s ) at 298 K
(set = 0 by convention). 30
i
• ab represents the variation of H Pb( s ) with temperature in the range 298 ≤ T ≤ 600 K,
T
20 Pb (l)
where H Pb( s ) , T is given by ∫298 c p, Pb( s ) dT .
h
• ac represents the variation of H 1 O2 ( g ) with temperature in the range 298 < T < 10 1/2O 2(g) c

Enthalpy, H, kJ
2
T Pb (s) b
3000 K, where H 1 O2 ( g ) is given by 12 ∫298 c p,O2 ( g ) dT . a
2
• ad is Δ H PbO( s ),298 K = – 219,000 J. 0
• de represents the variation of H PbO( s ) with temperature in the range 298 K ≤ T ≤ –180 e
T
1159 K, where H PbO(s ),T = −219, 000 + ∫298 c p, PbO(s ) dT J .
–190
In Figure 6.7b:
PbO (s
)
–200
• a represents the enthalpy of 1/2 mole of O2( g ) and 1 mole of Pb( s ) at 298 K.
• f represents the enthalpy of 1/2 mole of O2( g ) and 1 mole of Pb( s ) at the temperature T. –210
d
• g represents the enthalpy of 1 mole of PbO( s ) at the temperature T .
–220
300 500 700 900 1100
Temperature, K
(a)

Figure 6.7a (a) The variation, with temperature, of the enthalpies of Pb( s ) , Pb( l ) , 1/2
PbO( s ) .
HPbo(298) = –219,000 J/K
cp,Pb(s) = 23.6 + 9.75 × 10–3T J/K from 298 K to Tm,Pb
Thermochemistry
cp,Pb(l ) = 32.4 – 3.1 × 10–3T J/K from Tm,Pb to 1200 K
cp,PbO(s) = 37.9 + 26.8 × 10–3T J/K from 298 K to Tm,Pbo
cp,O2(g) = 29.96 + 4.18 × 10–3T – 1.67 × 105T–2 J/K from 298 K to 3000 K
The variation of heats of chemical reaction
HEAT CAPACITY, (or heats
ENTHALPY, of formation) with
ENTROPY
∆Hm,Pb = 4810 J at Tm,Pb = 600 K
temperature
Tm,PbO = 1159 K
at constant pressure can be represented on an enthalpy–
50
temperature diagram T T’
40 l
)
• a represents the enthalpy of 1/2 mole of oxygen gas and301 mole of Pb( s ) at+ 1298 /2O K
2(g

Pb
(set = 0 by convention). 20 k
• ab represents the variation of H Pb( s ) with temperature in the 10
range 298
f
≤ Tj ≤ 600 K,

Enthalpy, H, kJ
T
where H Pb( s ) , T is given by ∫298 c p, Pb( s ) dT . a
0
• ac represents the variation of H 1 O2 ( g ) with temperature in the range 298 < T <
2 –180 e
T
3000 K, where H 1 O2 ( g ) is given by 2 ∫298 c p,O2 ( g ) dT .
1
2 –190
• ad is Δ H PbO( s ),298 K = – 219,000 J.
PbO (s
)
• de represents the variation of H PbO( s ) with temperature in the range 298 K ≤ T ≤
–200
T
1159 K, where H PbO(s ),T = −219, 000 + ∫298 c p, PbO(s ) dT J . –210 g
d
–220
In Figure 6.7b: 300 500 700
Temperature, K
900 1100

(b)
• a represents the enthalpy of 1/2 mole of O2( g ) and 1 mole of Pb( s ) at 298 K.
• f represents the enthalpy of 1/2 mole of Figure
O2( g ) and
6.7b 1(b)
mole of Pb( s )with
The variation, at the temperature
temperature, T.
of the enthalpies of (Pb + 1/2O ) a 2

• g represents the enthalpy of 1 mole of PbO( s ) at the temperature T .


Table 6.1 Thermochemical Data for Pb, PbO, and O2
UCTION TO THE THERMODYNAMICS OF MATERIALS, SIXTH EDITION
hus,

∆H PbO,298 K Thermochemistry
= ∆H (a → f ) + ∆H ( f → g) + ∆H ( g → d )
⎛1 T
⎞ 298
=

⎜ 2 c p,O2 ( g ) +OF
CTION TO THE THERMODYNAMICS
298 ⎝
c p,Pb

( s ) ⎟ dT + ∆HSIXTH
MATERIALS,

PbO,T +EDITION
c p,PbO(s )dT
The variation of heats of chemical reaction (or heats of formation) with
T
168 = ∆H (a → f ) + TO
INTRODUCTION ∆HTHE → g) + ∆H ( g OF
( f THERMODYNAMICS →MATERIALS,
d) SIXTH EDITION
d thus, temperature
T
⎛1 at constant ⎞ pressure can beCAPACITY,
298 HEAT represented on an enthalpy–
∫ ∫
ENTHALPY, ENTROPY
= temperature
Thus, ⎜ 2 c p,O2 ( g ) + diagram
c p,Pb( s ) ⎟ dT + ∆H
T PbO,T + c p,PbO(s )dT
298 ⎝
= ∆H (a → f ) + ∆H ( f →
T∆H PbO,298 K
∆HgT )=+ ∆∆H ⎠
H298( g+ → d∆) c p dT
= ∆H (a → f ) + ∆H ( f → g298
T
) + ∆298

H (g → d )
50

⎛1 ⎞ T T’

∫ ∫
40
here:= ⎜ 2 p,O2 ( g ) = p,Pb⎛ (1s )c⎟ dT ++∆c H PbO,⎞TdT+ + ∆H c p,PbO(
c + c T
s ) dT
298 l

∫ PbO,T +

)
298 ⎝ ⎜ ⎠p,O2 ( g ) p,Pb( s ) ⎟ T c p,PbO(s )dT 30 1/2O
2(g

298 ⎝ 2 ⎠ T Pb
+
T


1 20 k
and thus, ∆HT = ∆∆H = c+p,PbO( s ) ∆
c p298 −ccpp,dT
Pb ( s ) − c p , O2 ( g ) j
2 10 f

Enthalpy, H, kJ
298
T a


T


0
∆HTin=Table
From the data ∆H 298
6.1,+∆HT ∆
= c∆pHdT
298 + ∆c p dT
298 298 –180 e

where: –190
∆c p = −0.7 + 14.96 ×110 −3 T + 0.85 × 10 5 T −2
∆c p = c p,PbO( s ) − c p,Pb( s ) − c p,O12 ( g ) –200 PbO (
s)

and, thus, in the range of∆temperature c p2,Pb298


c p = c p,PbO1( s ) −from ( s ) − to c600
p,O ( K
g ) (T
m ,Pb ): –210
2
∆c pthe
In = c prange
, PbO ( s ) − cof s) − c p,O2 ( g ) 2from
p, Pb (temperature 298 to 600 K d
g

2 –220
n Table
From 6.1,
the data in Table 6.1, T
300 500 700 900 1100


Temperature, K
Table 6.1,∆HT = −219, 000 + (−0.7 + 14.96 × 10 −3 T + 0.85 × 10 5 T −2 )dT (b)
298 −3
∆c p = −0.7 + 14.96 × 10
−3 T + 0.855 × 1−02−53T −22
∆c p = −0.=7 −+219 000×−100.7(TT −+298
14,.96 ) +×
0.85 7.148
0 ×T10 (T − 298 2
) 6.7b
Figure (b) The variation, with temperature, of the enthalpies of (Pb + 1/2O 2 ) an
−3 −2
∆c pthus,
= −0in.7the
+ 14 × 1temperature
.96 of 0 T +10.85from
× 10 T 5
and, range 5⎛ 1 ⎞298 to 600 K (T m ,Pb ):
− 0.85 × 10 −
e range of temperature from⎜⎝ T298298 ⎟
to 600
⎠ K (T m ,Pb ): Table 6.1 Thermochemical Data for Pb, PbO, and O2
range of temperature from 298 to
T 600 K (T m ,Pb ):
−3 5 −2
HPbo(298) = –219,000 J/K
∆H 298 = H MO(s )298 − H M( s )298 − H O2 ( g )298
2
⎛1 1 ⎞
− 0.85 × 10 5 ⎜ − ⎟
⎝ T 298 ⎠ Thermochemistry and, since H M,298 and H O2 ,298 are by convention set equal to zero, then

∆H 298 = H MO,298

The variation of heats of chemical reaction (or heats of formation) with tempera
at constant pressure can be represented on an enthalpy– temperature diagram, s

T = 500IfK,
a phase change
this gives ∆ H 500occurs
= – in oneJ, or
217,800 as more
can be of theinreactants
seen Figures or and
6.7b products,
as those in Figure 6.7a and b, which are drawn for the oxidation reaction
K
between the two temperatures at which the reaction
f a phase change occurs in one or more of the reactants or products, between is being Pb + considered,
1
2
O = PbO 2

then theatenthalpies
wo temperatures of transformation
which the reaction of the then
is being considered, phase thechanges
enthalpiesmust of be
The pertinent thermochemical data for this system are listed in Table 6.1.
In Figure 6.7a:
ormation of the phase changes must be considered. In Figure 6.7a, h represents
considered 50
thalpy of 1 mole of Pb( l ) at the melting temperature of 600 K, given as 40

30
i
h represents the enthalpy of 1 mole600 of Pb(l) at the melting Pb (l)


20

Pb ( l ),600 K = c p,Pb( s ) dT + ∆H m,Pb


temperature of H600 K 10
h
1/2O 2(g) c

Enthalpy, H, kJ
Pb (s) b
298 a
0

bh is the enthalpy of melting of Pb at the melting temperature –180 e

he enthalpy
of 600ofK,melting of Pb at the
and hi represents the melting
variation temperature
of the enthalpyofof600
1 K (= 4810
–190
J), and O (s)
Pb
mole of Pb(l) with temperature in the range 600–1200 K.
resents the variation of the enthalpy of 1 mole of Pb( l ) with temperature in the
–200

–210
600– 1200 K. –220
d

300 500 700 900 1100


Temperature, K
(a)
600 T
H Pb(l ),T =

298
c p, Pb( s ) dT + ∆H m, Pb +

600
c p, Pb(l ) dT
Figure 6.7a (a) The variation, with temperature, of the enthalpies of Pb( s ) , Pb( l ) , 1/2O2( g ) ,
PbO( s ) .

ure 6.7b, ajkl represents the variation of the enthalpy of 1 mole of Pb and 1/2
of O2( g ) , and hence, ∆HT ’ is calculated from the cycle
Thermochemistry
ajkl
CAPACITY, representsENTROPY
ENTHALPY, the variation
of the enthalpy of 1 mole of Pb and 1/2
169moles of O2(g), and
CAPACITY, ENTHALPY, ENTROPY 169
hence, ∆HT is calculated from the cycle
HEAT CAPACITY, ENTHALPY, ENTROPY

∆H 298 K = ∆H ( a → d ) = ∆H ( a → j ) + ∆H ( j → k ) + ∆H ( k → l )
∆H 298 K = ∆H ( a → d ) = ∆H ( a → j ) + ∆H ( j → k ) + ∆H ( k → l ) 50
+ ∆H ( l → e ) + ∆H ( e → g ) + ∆H ( g → d ) 40
T T’

+ ∆H ( l → e ) + ∆H ( e → g ) + ∆H ( g → d )
l
)
2(g
30 /2O
where: Pb
+ 1

where: 20 k
Tm ,Pb
⎛ 1 ⎞

j
∆H (a → j ) = +
⎜ p, Pb( s ) 2 pO2 ( g ) ⎟ dT
c c 10 f

Enthalpy, H, kJ
298Tm ,⎝Pb ⎛ 1 ⎠ ⎞ a
∆H (a → j ) =
∫ ⎜c
∆H ( j → k ) = the latent 298
+ c
2 ⎟ dT
p, Pb ( s )
⎝ heat of melting of⎠ Pb at T
pO 2 ( g )
m , Pb = 4810 J
0

–180 e

∆H ( j → k ) = Tthe⎛latent heat
1 of melting
⎞ of Pb at Tm, Pb = 4810 J –190

∆H (k → l ) =
∫ T ⎝
Tm ,Pb
⎜ c p, Pb(l ) + 2 c p,O2 ( g ) ⎟ dT
⎛ 1 ⎠ ⎞
–200 PbO (
s)

∆∆HH(l(k→→
e)l=) = ∫
∆HT ⎜ c p, Pb(l ) + 2 c p,O2 ( g ) ⎟ dT
Tm ,Pb
Tm ,Pb
⎝ ⎠
–210

–220
d
g


300 500 700 900 1100
∆∆HH(e(l→
→ge))== ∆HTc p, PbO(s ) dT Temperature, K
T (b)
Tm ,Pb

∆H ( g → d ) = ∫
∆H (e → g) = 298
c dT
∫ T
Tm ,Pb
298
p, PbO(s )
c p, PbO ( s ) dT Figure 6.7b (b) The variation, with temperature, of the enthalpies of (Pb + 1/2O 2 ) an

Thus,
∆H ( g → d ) =
∫Tm ,Pb
c p, PbO( s ) dT Table 6.1 Thermochemical Data for Pb, PbO, and O2
HPbo(298) = –219,000 J/K
∆H∆(H
l→( ge)→
= ∆dH)T=
∫ c p, PbO( s ) dT

Thermochemistry
Tm ,Pb Tm ,Pb
∆H (e → g) =
∫ T
c p, PbO(s ) dT
Thus, 298
∆H ( g → d ) =
∫ Tm ,Pb
c p, PbO( s ) dT

⎛ Tm ,Pb
1 ⎞
Thus, ∆HT = ∆H 298 K +
298 ⎝ ∫ c
⎜ p, PbO( s ) − c p, Pb ( s ) − c , O2 ( g ) ⎟ dT
HEATpCAPACITY,
2 ⎠
ENTHALPY, ENTROPY

T
⎛ T ⎛ 1 ⎞ 1 ⎞

∫m298,Pb +⎝ Tm,Pb ⎜⎝ c p,PbO(s) 2− c p,Pb(l⎠) − 2 c p,O2 (g) ⎟⎠ dT 40
m ,Pb
50
∆HT = ∆H−
298∆ +
K H ⎜ c p , PbO ( s ) − c p , Pb ( s ) − c p , O
2 ( g ) ⎟ dT T T’
l
)
⎛ T
1 ⎞ 2(g

= −219, ∫000 +
30 /2O
− ∆H m, Pb + c 6 0 0 − c − c p,O2 ( g ) ⎟ dT + 1

∫ (−0.7 + 14.96 × 10 T + 0.85 × 10 T )dT


⎜ p, PbO( s ) p, Pb ( l ) Pb
Tm ,Pb ⎝ 2 ⎠ −3 520 −2 k
600 298 j


10 f

Enthalpy, H, kJ
−3 −2
= −219, 000 + (−T 0.7 + 14.96 × 10 T + 0.85 × 10 T )dT 5
a


298 −3 −2 0
− 4810 + (−9.3 + 27.8 × 10 T + 0.85 × 10 T )dT
T
5


–180 e
− 4810 + 3 + 27.8 × 10 −3 T + 0.85 × 10 5 T −2 )dT
(−9.600
600 –190

PbO (
s)

givesΔ H
gives Δ1000
H 1000 = – 216,700
= – 216,700 J at T' J= at T' K,= as
1000 1000 K,inasFigures
is seen is seen6.7binand
Figures
6.8. 6.7b and 6.8. –200

re6.8
re 6.8shows
shows
the the variation
variation of TΔwith
of Δ H PbO, H PbO, with
temperature
T temperature
in the range in
298– the
1100
–210
range
K. d 298– g
1100 K.
–220
ee temperature
temperature of interest is higher
of interest is than
higherthe melting
than the temperatures of both the metal
melting temperatures of
300 both
500 the metal
700 900 1100
its oxide, then both enthalpies of melting must be considered. For example,(b) with Temperature, K
its oxide, then both enthalpies of melting must be considered. For example, with
ence to Figure 6.9, which is drawn for the general oxidation,
ence to Figure 6.9, which is drawn for the general oxidation,
Figure 6.7b (b) The variation, with temperature, of the enthalpies of (Pb + 1/2O ) an 2
1
M + O2 = MO
2 1 Table 6.1 Thermochemical Data for Pb, PbO, and O2
M+ O2 = MO HPbo(298) = –219,000 J/K
600


= −219, 000 +
(−0.7 + 14.96 × 10 T + 0.85 × 10 T )dT −3

Δ H 1000 = – 216,700 J at T' = 1000 K, as is seen in Figures 6.7b and 6.8.


5 −2

Thermochemistry
298
–224
T 300 500 700 900 1100

∫ (−of9.3Δ+H27PbO,
shows the−variation T with
T + 0temperature
.85 × 10 T )dT in the range 298– 1100 K.
−3 −2
4810 + .8 × 10 5
Temperature, K
600
erature of interest is higher than the melting temperatures of both the metal
de, then
gives both
Δ H 1000
If enthalpies
= – 216,700
the J at T'of
temperature melting
= of
1000 K, as must
interestis is
seen be
in considered.
Figure 6.8 The and
Figures
higher than6.7b For
variation,
the=melting
1/2O PbO.
example,
6.8. with with of both the metal and its
temperature, of the enthalpy change for the reaction Pb +
temperatures
6.8 shows the variation of Δ H PbO, T with temperature in the range 298– 1100 K.
2

oe Figure 6.9, which


oxide, then isboth
drawn for the general
enthalpies oxidation,
temperature of interest is higher than the meltingoftemperatures
melting must
of bothbe
the considered.
metal
ts oxide, then both enthalpies of melting must be considered. For example, with
1 general oxidation,
ence to Figure 6.9, which is drawn for the
M+ O2 = MO
1 2
M+ O2 = MO
2 O 2(g)
M (l) + 1/2
⎛ Tm ,M
1 ⎞

∆HT = ∆H 298 + T ⎛ ⎜ c p, MO( s ) − c p1, M( s ) −⎞ c p,O2 ( g ) ⎟ dT
∫298 ⎝
m ,M
∆HT = ∆H 298 + 298⎜ c p⎝, MO( s ) − c p, M( s ) − c p,O ( g ) ⎟ 2
2 ⎠
dT ⎠2 DHm,M
DHT
O 2(g )
+ 1/2
c p,⎛MO(s ) − c p, M(l ) − c p,O ( g ) ⎟ dT ⎞
Tm ,T
m ,⎛MO 1 ⎞1
− ∆H m, M +∫T ⎝ ⎜ c p, MO(s ) − c2p, M(l ) −⎠ c p,O2 (0g ) ⎟ dT
M (s)


MO
MO (l)

Enthalpy
− ∆H m, M + ⎜ 2

Tm ,M ⎝ 2 ⎠
m ,M

T
⎛ 1 ⎞

DHm,MO
+ ∆H m, MO + ⎜ c p, MO(l ) − c p, M(l ) − c p,O2 ( g ) ⎟ dT DH298
Tm ,MO ⎝ ⎛ ⎠ 1 ⎞
T 2
+ ∆H m, MO +
∫ Tm ,MO
⎜⎝ c p , MO ( l ) − c p , M(l ) −
2
c p , O 2 ( g ) ⎟⎠ dT MO (s)

298 Tm,M Tm,MO T


Temperature

Figure 6.9 The effect of phase changes on Δ H for a chemical reaction.


Adiabatic Flame Temperature
Maximum temperature of the flame that can be achieved theoretically
when fuel is burned

Assuming adiabatic conditions of burning we can find out the


temperature that the flame can achieve

Whatever heat is liberated in the combustion of constituents that are


present shall be available to raise the temperature of the products that
make the flame

Reactants at T1 burning Products at T2


Adiabatic Flame Temperature
Reactants at T1 burning Products at T2

C + O2 = CO2
2H + 1/2O2 = H2O

CO2 and H2O are the combustion reactions then the products can be
ascertained from the composition of the fuel and amount of air and or
oxygen supplied for its burning

T1
ΔH = ∫ [C P (CO2 ).nCO2 + CP (H 2O).nH 2O + CP (O2 ).nO2 + CP (N 2 ).nN2 ]dT
298

The temperature rise of the product can thus be calculated from these
knowing the mass of the reactants and the products and the Cp values
for CO, CO2 ,H2O, etc. be known for that temperature range.
Conclusions from 1st law

1. Energy cannot be created nor can it be destroyed, it changes only its form
2. Energy can be interconverted.
3. Although the first law as such does not impose any limitation on such interconversion
and as is observed in practice, that mechanical work can be fully converted to heat energy, yet out
of all conceivable changes, only some actually occur in practice in fully converting the form,
whereas many others do not do so.
4. There is a certain tendency for the conversion of energy to occur in some preferential direction
rather than for either direction to be equally possible.
MM209 - Thermodynamics
Instructor : Aswani Yella
2nd law of thermodynamics
First law → law of conservation of energy → universally accepted as soon as it was
stated → because it appeared reasonable and in accord with human intuition.

Second law → law of degradation of energy → developed simultaneously to first law


through work of Carnot, Clausius and Kelvin → Came as a new thing → alien to
traditional thought.

Second law together with the first law lays the foundation for the thermodynamic
method of describing the behaviour of matter

First law → Simply states that total energy of an isolated system is constant

Left to itself, a system will do one of the two things

1.  It will remain in the state in which it happens to be (or)


2.  It will move of its own accord to some other state
2nd law of thermodynamics
•  If the system is in equilibrium with surroundings, → left to itself, → it will remain the
same.

•  If the initial state is not in equilibrium with surroundings → left to itself → it will
spontaneously move towards equilibrium.

•  So something happen naturally and something's don’t

•  Some systems if they are in equilibrium does not change at all and some system
changes spontaneously. It is a matter of everyday experience that there is a
definite directions for spontaneous processes.
2nd law of thermodynamics

Eg:- System A → Decrease in ‘T’ on a hot object with respect to surroundings



Inverse does not take place spontaneously

Hot object → Decrease in internal energy of the body and increase in internal
energy of surroundings.

Inverse process → energy could be conserved → but does not happen

Internal energy of surroundings would not decreases spontaneously and warm the
body.
to its initial temperature.

Read BS, Chapter 7


Atmospheric air
Q
at T0and energy are fine concepts that allow us to quantify and predict well
Conservation of mass
many phenomena which are observed in nature. And if a phenomenon can be repeated, it
becomes subject to prediction, and can be thought of as a science.
However, conservation of mass Time
and energy, by themselves,Time
admit as possibilities phenom-
Body at T0 < T < Ti T0
ena which are not observed
Ti > T0 in nature! For instance consider an isolated system composed of
two equal masses of liquid water. See Fig. 7.1. The first is at TA = 310 K, the second is at

(a)
Atmospheric air A B
at p0
Valve T = 320 K T = 280 K

Air at B Air
A
pi > p0 Air at
not observed in nature
p0 < p < pi p0
T = 310 K T = 290 K t ∞

(b) A B

T = 300 K T = 300 K

observed in nature
Body at Time Time
T0 < T < Ti T0
Ti > T0
System B → Air held at high pressure move towards low pressure surrounds when the
valve is opened.
(a)
Atmospheric air
at p0
Valve

Air at Air
pi > p0 Air at
p0 < p < pi p0

(b)
Air held at a higher pressure moves towards lower pressure
(b)

Mass
Mass
zi
0 < z < zi Mass

(c)elevation falls when released


Mass suspended at an

PE of the mass → converted to internal energy of surroundings

Inverse process → Mass would not return to its initial elevation spontaneously while
internal energy of surroundings decrease.
2nd law of thermodynamics
In all the cases above, the initial conditions can be restored.

è  An object can be cooled, a gas can be confined to smaller volume or mass can be
brought to initial elevation ‘but’ not in “spontaneous” process.

Some Auxiliary devices are needed



In each cases, a fuel or electrical input would be required for the device to function so
that a permanent change in surroundings be bought
2nd law of thermodynamics
Not every process that is consistent with energy conservation can occur.

Also energy conservations does not predict the preferred direction and it does not permit the
process that can occur to be distinguished from those that cannot.

1st law does not predict how fast/slow a system reached equilibrium
Eg:- Some chemical reactions → Instantaneously

Melting of ice at RT → few minutes All processes follows first law

Iron bar rusting → few years

But insufficient to predict the final equilibrium state,

So, a general principle required and that is second law.


2nd law of thermodynamics
Some aspect of the world determines the spontaneous direction of change, the
direction that does not require what to bring the change.

So what determines the direction of spontaneous change?

Is it “Total energy" of the system?

we cannot say that everything tends towards a state of lower energy because total
internal energy of an isolated system is constant.

It is the energy of the system that tends towards maximum? No → based on two
arguments

1. Perfect gas expands spontaneously to vacuum yet it is internal energy remains


constant

2. If the energy of the system does decrease during spontaneous then the energy of the
surroundings also should increase by the same amount and just as spontaneous.

Therefore, when change occurs, internal energy of an isolated system remains constant
but it is parcelled out in many ways.
2nd law of thermodynamics
Can it be therefore, that the direction of change is related to distribution of energy?

This idea is the key and that spontaneous changes are always accompanied by
dispersal of energy.

The role of the distribution of energy can be understood


by thinking about a ball (the system) bouncing on a floor
(the surroundings)

The direction of spontaneous change is towards a state


in which the ball is at rest with all its energy dispersed
into disorderly thermal motion of molecules in the air and
of the atoms of the virtually infinite floor
2nd law of thermodynamics
A ball resting on a warm floor has never been observed to start bouncing

some of the thermal motion of the atoms in the floor would


have to accumulate in a single, small object, the ball

This accumulation requires a spontaneous


localization of energy from the myriad vibrations of
the atoms of the floor into the much smaller number
of atoms that constitute the ball

The thermal motion is random, for the ball to move


upwards its atoms must all move in the same
direction. The localization of random, disorderly
motion as concerted, ordered motion is so unlikely
that we can dismiss it as virtually impossible

The reverse has never been observed to take place on a macroscopic scale.
2nd law of thermodynamics
Signpost
96 of 3spontaneous change: we need96to look
THE SECOND LAW
3 THE
for the direction
SECOND LAWof change that
leads to dispersal of the total energy of the isolated system.
is spread out
is spread out as thermal motion of the atoms of the fl
spontaneous
spontaneous because it is highly improbable that
leading to un
leading to uniform motion of the ball’s atoms. A gas d
because to do
because to do so the random motion of its molecules,
tion of kineti
tion of kinetic energy throughout the container, woul
same region
same region of the container, thereby localizing the
spontaneous
spontaneous expansion, is a natural consequence of en
as the gas m
as the gas molecules occupy a larger volume. An o
become warm
become warmer than its surroundings because it is hig
of randomly
(a)of randomly vibrating (b) atoms in the surroundings will
(a) (b) mal motion
mal motion in the object. The opposite change, the s
into the surr
A ballFig.resting Fig.For
into
3.3 the
the
The ball to
molecular fly
surroundings upwards,
as some
thermal
interpretation of of
motion,
the the is natural.
3.3 Theon a warm
molecular surface; the
interpretation of the It may see
atomsirreversibility
are undergoing thermal motionLaw. random
irreversibility
It may vibrational
expressed
seem verybymotion
the
puzzling would
Second
thatLaw. have
the to
spreading out o
expressed by the Second the formatio
(a)change
A ball
the into on
resting
formation coordinated,
a warm
of directed
surface;
such ordered the motion.
structures as crystals o
(a) A ball resting on a warm surface; the course, we sh
atoms are undergoing
course, we shall thermal
see that motion of energy and matt
dispersal
atoms are undergoing thermal motion forms.
(vibration, in this instance), as indicated by
(vibration, in this instance), as indicated by forms.
Such a conversion is highly improbable
the arrows. (b) For the ball to fly upwards,
the arrows. (b) For the ball to fly upwards,
some of the random vibrational motion
some of the random vibrational motion 3.2 Entrop
would have to change into coordinated,
would Entropy
3.2 have to change into coordinated,
2nd law of thermodynamics
A process which involves the spontaneous movement of a system from non-equilibrium
state to an equilibrium state is called a natural/spontaneous/real process .

Such process cannot be reversed naturally less an external source is used → hence
termed “IRREVERSIBLE”

There are many factors that make processes irreversible

(E.g.)
1. Heat transfer through a finite temperature difference
2. Unrestrained expansion of a gas/ liquid
3. Spontaneous chemical reactions
4. Spontaneous mixing
5. Friction
6. Electric current flow through a resistor
7. Magnetization/ polarization with hysteresis
8. Inelastic deformation

All actual processes are Irreversible and the term irreversibility is used to define any of
these effects
2nd law of thermodynamics
Limit of actual realisable processes → Processes that is perfectly executed.

A Irreversible processes is the limiting case as irreversibilities are reduced further and further.

If a process, is reversible → Concept of spontaneity is no longer applicable

•  Spontaneity occurred as a result of the system moving from non-equilibrium state to equilibrium
state

If the spontaneity is removed, the system can be made reversible

At all times during the process the system is at equilibrium (never far from equilibrium)

Passes through a continuous equilibrium states

Of course imaginary, but it is possible to conduct and actual process such that it is virtually
reversible.

Process proceeds through infinitesimally small driving force such that the system is never more
than infinitesimal distance from equilibrium.
2nd law of thermodynamics
If a system undergoes a spontaneous process involving the performance of work and
the transfer of thermal energy, then, as the process continues, during which time the
system approaches its equilibrium state, the capacity of the system for further
spontaneous change decreases, as does its capacity to do further work

Once equilibrium is reached, the capacity of the system for doing further work is
exhausted

As a result of the spontaneous process, the energy of the system has become
degraded

Energy which was available for doing useful work, is now in a form which is not
available for external purposes

Dissipation of energy.
2nd law of thermodynamics

Actual process → always Irreversible → there could be an ideal processes which


although never occurring in nature, is imaginable.

Such ideal process→ reversible process → Friction, electric resistance or other such
sources of dissipation are eliminated.

No dissipation/ degradation of energy


2nd law of thermodynamics
Since the degree of irreversibility of a process is path dependent, it should be possible
for the process to be conducted in such a manner that the degree of irreversibility is
minimized.

The ultimate of this minimization is a process in which the degree of irreversibility is


zero and in which no degradation of energy occurs.

This limit, which the behavior of real systems can be made to approach, is called a
reversible process.

A reversible process, then, is one during which the system is never away from
equilibrium.

A reversible process which takes the system from the state A to the state B is one in
which the process path passes through a continuum of equilibrium states. Such a path
is, of course, an idealization, but it is possible to conduct an actual process in such a
manner that it is virtually reversible.
2nd law of thermodynamics
Such an actual process (sometimes called a quasi-static process) is one which proceeds
under the influence of an infinitesimally small driving force, such that, during the process,
the system is never more than an infinitesimal amount from equilibrium.

If, at any point along the path, the small external influence is removed, then the process
ceases; if the direction of the small external influence is reversed, then the direction of
the process is reversed.
2nd law of thermodynamics
46 Introduction to the Thermodynamics of Materials
Consider a system of water and water vapor at the uniform temperature
3.5 AN ILLUSTRATION T contained
OF IRREVERSIBLE in
AND REVERSIBLE
a cylinder fitted with a frictionless piston, and let the cylinder be placed in thermal
PROCESSES

contact with a heat reservoir which is also at the constant temperature


Consider a system T. at the uniform temperature T contained
of water and water vapor
cylinder fitted with a frictionless piston, and let the cylinder be placed in thermal contact w
heat reservoir which is also at the constant temperature T. This system is shown in Fig

The water vapor in the cylinder exerts a certain


pressure PH2O(T), which is the saturated vapor pressure
of water at the temperature T.

The system is exactly at equilibrium when the external


pressure acting on the piston, Pext, equals the internal
pressure acting on the piston,PH2O(T) and when the
temperature of the water+ water vapor in the cylinder
equals the temperature of the constant temperature
heat reservoir Figure 3.2 A thermostalled piston and cylinder containing water and
water vapor.

The water vapor in the cylinder exerts a certain pressure , which is


saturated vapor pressure of water at the temperature T. The system is exactly
equilibrium when the external pressure acting on the piston, Pext, equals the inte
pressure acting on the piston, , and when the temperature of the water+w
!d: \‡ p…A‡‡”…A —\__ )A _g—A…8 :AA…b\dA: )™ YA !bg‡pYA…\2 p…A‡‡”…A !d
—A\QY gJ YA
ndp\‡gdu  \‡ A–Ad pg‡‡\)_A46 Y! :”…\dQ Y\‡ A˜p!d‡\gd YA p\‡gd
2 law of thermodynamics Introduction to the Thermodynamics of Materials
g–A…‡Ygg \‡ ”_\b!A pg‡\\gd8 YAd :…gp3.5)A_g— AN ILLUSTRATION \8 !d: !JA… ‡gbA
OF IRREVERSIBLE g‡2\__!
AND REVERSIBLE
PROCESSES
‡A_A :g—d g \‡ Kd!_ pg‡\\gdu rYAYA… Y\‡ !2”!__™ Y!ppAd‡ \d ! Q\–Ad
Consider a system of water and water vapor at the uniform temperature T contained
If the external pressure acting on the piston, Pext is suddenly
cylinder fitted with decreased
a frictionless piston, andby
let theacylinder
finite be placed in thermal contact w
amount ΔP, then the imbalance in pressure causes the piston to accelerate rapidly out
heat reservoir which is also at the constant temperature T. This system is shown in Fig

of the cylinder.

The consequent rapid expansion of the water vapor


decreases the water vapor pressure to a value below its
saturation (and hence equilibrium) value, and thus water
spontaneously evaporates in an attempt to reestablish
equilibrium between the water and its vapor.

Figure 3.2 A thermostalled piston and cylinder containing water and


water vapor.
The spontaneous evaporation, being endothermic, decreases the temperature of the
water, and hence sets up a temperature gradient between the heat reservoir and the
The water vapor in the cylinder exerts a certain pressure
saturated vapor pressure of water at the temperature T. The system is exactly
, which is

contents of the cylinder. This, in turn, causes heat toequilibrium


flow spontaneously fromon the
when the external pressure acting heat
the piston, Pext, equals the inte

reservoir to the cylinder in an attempt to reestablish vapor


thermal equilibrium between
pressure acting on the piston,
the two
, and when the temperature of the water+w
in the cylinder equals the temperature T of the constant-temperature heat reserv
If the external pressure acting on the piston, Pext is suddenly decreased by a finite amo
P, then the imbalance in pressure causes the piston to accelerate rapidly out of
!d: \‡ p…A‡‡”…A —\__ )A _g—A…8 :AA…b\dA: )™ YA !bg‡pYA…\2 p…A‡‡”…A !d
—A\QY gJ YAndp\‡gdu  \‡ A–Ad pg‡‡\)_A46 Y! :”…\dQ Y\‡ A˜p!d‡\gd YA p\‡gd
2 law of thermodynamics Introduction to the Thermodynamics of Materials
g–A…‡Ygg \‡ ”_\b!A pg‡\\gd8 YAd :…gp3.5)A_g— AN ILLUSTRATION \8 !d: !JA… ‡gbA
OF IRREVERSIBLE g‡2\__!
AND REVERSIBLE
PROCESSES
‡A_A :g—d g \‡ Kd!_ pg‡\\gdu rYAYA… Y\‡ !2”!__™
If, when 1 mole of water has evaporated, the external pressure acting on the piston is
Y!ppAd‡ \d ! Q\–Ad
Consider a system of water and water vapor at the uniform temperature T contained
instantaneously increased to the original value, P , then evaporation of the water
cylinder fitted with a frictionless piston, and let the cylinder be placed in thermal contact w
ext
heat reservoir which is also at the constant temperature T. This system is shown in Fig
vapor ceases, the flow of heat ceases, and compete equilibrium is reestablished.

The work done by the system during this


process equals (Pext– ΔP)V, where V is the
molar volume of
water vapor at .

If the external pressure acting on the piston is


suddenly increased by a finite amount ΔP, then the
piston accelerates rapidly into the piston

If, when 1 mole of water vapor has been condensed, Figure the external pressure
3.2 A thermostalled acting
piston and cylinder on water and
containing
water vapor.
the piston is instantaneously decreased to its original value, equilibrium is reestablished
, which is
and the work done on the system equals (Pext+ ΔP)V The water vapor in the cylinder exerts a certain pressure
saturated vapor pressure of water at the temperature T. The system is exactly
equilibrium when the external pressure acting on the piston, Pext, equals the inte
pressure acting on the piston, , and when the temperature of the water+w
The permanent change in the external agency caused by the cyclic process is thus 2ΔPV.
vapor in the cylinder equals the temperature T of the constant-temperature heat reserv
If the external pressure acting on the piston, Pext is suddenly decreased by a finite amo
P, then the imbalance in pressure causes the piston to accelerate rapidly out of
!d: \‡ p…A‡‡”…A —\__ )A _g—A…8 :AA…b\dA: )™ YA !bg‡pYA…\2 p…A‡‡”…A !d
—A\QY gJ YA
ndp\‡gdu  \‡ A–Ad pg‡‡\)_A46 Y! :”…\dQ Y\‡ A˜p!d‡\gd YA p\‡gd
2 law of thermodynamics Introduction to the Thermodynamics of Materials
g–A…‡Ygg \‡ ”_\b!A pg‡\\gd8 YAd :…gp3.5)A_g— AN ILLUSTRATION \8 !d: !JA… ‡gbA
OF IRREVERSIBLE g‡2\__!
AND REVERSIBLE
PROCESSES
‡A_A :g—d g \‡ Kd!_ pg‡\\gdu rYAYA… Y\‡ !2”!__™ Y!ppAd‡ \d ! Q\–Ad
Consider, again, the evaporation process. If the magnitude of Pext ispiston,
cylinder fitted with a frictionless
decreased by an
Consider a system of water and water vapor at the uniform temperature T contained
and let the cylinder be placed in thermal contact w
infinitesimal amount δP, the resulting minute imbalance between
heat reservoir which is also atthe pressures
the constant temperature T.acting
This system is shown in Fig

on the piston causes the cylinder to move slowly out of the piston.

The smaller the value of δP, then the


slower the process, the smaller the degree
of undersaturation of the water vapor, and
the smaller the temperature gradient.

The more slowly the process is carried out, then the


greater the opportunity afforded to the evaporation and
heat flow process to “keep up” with equilibrium
  ‘u‘ YA p…A‡‡”…A \dFigure YA3.2Q!‡ \d YA p\‡gd r!s \‡ :AA…b\dA:
A thermostalled piston and cylinder containing water and
pg—:A… \d YA p!du J YA …!™ \‡ …Abg–A: water vapor. YA Q!‡ A˜p!d:‡ ‡”::Ad_™ !d:

g ! Kd!_ ‡!A r)su J YA Q!‡The


A˜p!d:‡
water vapor ‡_g—_™8
in the cylinder)™ …Abg–\dQ
exerts gdA p!…\2_A
a certain pressure , which isg
saturated vapor pressure of water at the temperature T. The system is exactly
YA p…g2A‡‡ \‡ …A–A…‡\)_A r2su equilibrium when the external pressure acting on the piston, P , equals the inte
ext
pressure acting on the piston, , and when the temperature of the water+w
vapor in the cylinder equals the temperature T of the constant-temperature heat reserv
If the external pressure acting on the piston, Pext is suddenly decreased by a finite amo
P, then the imbalance in pressure causes the piston to accelerate rapidly out of
!d: \‡ p…A‡‡”…A —\__ )A _g—A…8 :AA…b\dA: )™ YA !bg‡pYA…\2 p…A‡‡”…A !d
—A\QY gJ YA
ndp\‡gdu  \‡ A–Ad pg‡‡\)_A46 Y! :”…\dQ Y\‡ A˜p!d‡\gd YA p\‡gd
2 law of thermodynamics Introduction to the Thermodynamics of Materials
g–A…‡Ygg \‡ ”_\b!A pg‡\\gd8 YAd :…gp3.5)A_g— AN ILLUSTRATION \8 !d: !JA… ‡gbA
OF IRREVERSIBLE g‡2\__!
AND REVERSIBLE
PROCESSES
‡A_A :g—d g \‡ Kd!_ pg‡\\gdu rYAYA… Y\‡ !2”!__™
If, after the evaporation of 1 mole of water, the external pressure is instantaneously
Y!ppAd‡ \d ! Q\–Ad
Consider a system of water and water vapor at the uniform temperature T contained
increased to its original value Pext, then the work done by the system equals (P – δP)V.
cylinder fitted with a frictionless piston, and let the cylinder be placed in thermal contact w
heat reservoir which is also at the constant temperatureext T. This system is shown in Fig

If the external pressure is then


increased by P, then work (Pext+ δP)V, is done on the
system to condense 1 mole of
water vapor, and the permanent change in the external
agency equals the work done on the system minus the
work done by the system during the cyclic process

The smaller the value of δP, then the more nearly equal
are the two work terms, and in the limit that they are
 
equal, no permanent change ‘u‘inYA
occurs p…A‡‡”…A \dFigure
the external YA3.2Q!‡ \d YA p\‡gd r!s \‡ :AA…b\dA:
A thermostalled piston and cylinder containing water and
agency, and hence the cyclic
pg—:A… process has been
\d YA p!du J YA …!™ \‡ …Abg–A:
water vapor. YA Q!‡ A˜p!d:‡ ‡”::Ad_™ !d:

conducted reversibly. g ! Kd!_ ‡!A r)su J YA Q!‡The


A˜p!d:‡
water vapor ‡_g—_™8
in the cylinder)™ …Abg–\dQ
exerts gdA p!…\2_A
a certain pressure , which isg
saturated vapor pressure of water at the temperature T. The system is exactly
YA p…g2A‡‡ \‡ …A–A…‡\)_A r2su equilibrium when the external pressure acting on the piston, Pext, equals the inte
pressure acting on the piston, , and when the temperature of the water+w
vapor in the cylinder equals the temperature T of the constant-temperature heat reserv
Complete reversibility is approached, only when the process becomes infinitely slow.
If the external pressure acting on the piston, Pext is suddenly decreased by a finite amo
P, then the imbalance in pressure causes the piston to accelerate rapidly out of
2nd law of thermodynamics
ENTROPY AND THE QUANTIFICATION OF IRREVERSIBILITY

Two distinct types of spontaneous processes are

1. The conversion of work into thermal energy—that is, the degradation of mechanical
energy to thermal energy (heat)
2. Flow of heat down a temperature gradient

An irreversible process is one in which the


energy of the system undergoing the process is
degraded

This means that there is a possibility that the extent of


degradation can differ from one process to another

So, a quantitative measure of the extent of degradation, or


degree of irreversibility, exists
2nd law of thermodynamics
Consider the weight–heat reservoir system
This system consists of a weight–pulley arrangement which is
coupled to a constant-temperature heat reservoir.
60 INTRODUCTION TO THE THERMODYNAMICS OF MATERIALS, S

The system is at equilibrium when an upward force acting on


the weight exactly balances the downward force, W, of the
weight.

If the upward force is removed, the equilibrium is upset and W


the weight spontaneously falls, performing work, which is
converted, by means of a suitable system of paddle wheels,
into thermal energy, which enters the constant-temperature
heat reservoir.
Figure 3.1 A weight– pulley– heat reservoir arrangement in which the work do
weight is degraded to thermal energy, which appears in the heat r

Equilibrium is reattained when the upward forceLewis


acting on the
and Randall * considered the following three processes:

weight is replaced, and the net effect of this process isheat


1. The thatreservoir in the weight– heat reservoir system is at the tempera
mechanical energy is converted to thermal energy. weight is allowed to fall, performing work, w, and the thermal energy p
enters the heat reservoir.
2. The heat reservoir at the temperature T 2 is placed in thermal contact w
2nd law of thermodynamics
Now consider the following three60processes:
INTRODUCTION TO THE THERMODYNAMICS OF MATERIALS, S

1.  The heat reservoir in the weight–heat reservoir


system is at the temperature T2. The weight is
allowed to fall, performing work, w, and the W
thermal energy produced, q, enters the heat Temperature T2
reservoir.

Figure 3.1 A weight– pulley– heat reservoir arrangement in which the work do
weight is degraded to thermal energy, which appears in the heat

Lewis and Randall* considered the following three processes:

1. The heat reservoir in the weight– heat reservoir system is at the tempera
weight is allowed to fall, performing work, w , and the thermal energy
enters the heat reservoir.
2. The heat reservoir at the temperature T is placed in thermal contact
2nd law of thermodynamics
TRODUCTION TO THE THERMODYNAMICS OF MATERIALS, SIXTH EDITION

2. The heat reservoir at the temperature


T2 is placed in thermal contact with
another heat reservoir at a lower
temperature T1, and the same thermal
W energy, q, is allowed to be transferred
Temperature T2 Temperature T1 from the reservoir at T2 to the reservoir
at T1.

0A weight–
INTRODUCTION TO THE
pulley– heat reservoir THERMODYNAMICS
arrangement in which the OF MATERIALS,
work SIXTH EDITION
done by the falling
T <T1
weight is degraded to thermal energy, which appears 2in the heat reservoir.

andall* considered the following three processes:

eat reservoir in the weight– heat reservoir system is at the temperature T 2 . The
t is allowed to fall, performing work, w , and the thermal energy produced, q ,
the heat reservoir.
eat reservoir at the temperature T 2 is placed in thermal contact with another
3. The heat reservoir in the weight–heat reservoir
eservoir at a lower temperature T 1 , and the same thermal energy, q , is allowedsystem is at the temperature T1. The weight is
transferred from the reservoir
W at T to the reservoir at T .
2
Temperature
eat reservoir in the weight– heat reservoir system is at the
1
temperature allowed to fall, performing work, w, and the
T1 T 1 . The
t is allowed to fall, performing work, w , and the thermal energy produced,thermal
q, energy produced, q, enters the reservoir.
the reservoir.

f these processes is spontaneous and hence irreversible , and therefore,


ngure
occurs in each of them. However, since process 3 is the sum of processes
3.1 A weight– pulley– heat reservoir arrangement in which the work done by the falling
e degradation occurring in process 3 must be greater than the degrada-
INTRODUCTION TO THE THERMODYNAMICS
60 OF MATERIALS,
INTRODUCTION
2nd law of thermodynamics
SIXTH EDITION
TO THE THERMODYNAMICS OF MATERIALS, SIXTH EDITION
60 INTRODUCTION TO THE THERMODYNAMICS OF MATERIALS, SIXTH E

W
W W Temperature T1
Temperature T2 Temperature T2 Temperature T1

Figure 3.1 A weight– pulley– heat reservoir arrangement in which the work done by th
weight is degraded to thermal energy, which appears in the heat reservoi
1 Figure
A weight– pulley– heat reservoir arrangement 3.1 Athe
in which weight–
workpulley–
done heat reservoir
by the fallingarrangement in which the work done by the falling
Each of these processes is spontaneous and hence irreversible, and therefore,
weight is degraded to thermal energy, which appearsweight
in theisheat
degraded to thermal energy, which appears in the heat reservoir.
reservoir.
Lewis and Randall* considered the following three processes:

d Randall*
degradation occurs
considered the following three Lewis
processes:
in each of them
and Randall considered the following three processes:
*
1. The heat reservoir in the weight– heat reservoir system is at the temperature T . 2
weight is allowed to fall, performing work, w , and the thermal energy produce
1. The
e heat reservoir in the weight– heat reservoir system heat
is at thereservoir in the weight–
temperature enters the heat reservoir.
T 2 . Theheat reservoir system is at the temperature T 2 . The
ight is allowed to fall, performing work, w , and the thermal energy produced, q , work, w , and the thermal energy produced, q ,
weight is allowed to fall, performing 2. The heat reservoir at the temperature T 2 is placed in thermal contact with ano
enters the heat reservoir. heat reservoir at a lower temperature T 1 , and the same thermal energy, q , is allo
Thermal energy transferred in all three cases is q
ers the heat reservoir.
e heat reservoir at the temperature T 2 is placed 2.in The heat reservoir
thermal contact atwiththe another
to be transferred from the reservoir at T 2 to the reservoir at T 1 .
temperature T 2 is placed in thermal contact with another
3. The heat reservoir in the weight– heat reservoir system is at the temperature T 1 .
Only difference is the temperature of the constant reservoir bath
at reservoir at a lower temperature T 1 , and the sameheat reservoir
thermal at a lower
energy,
to beattransferred
be transferred from the reservoir at T 2 to the reservoir T1.
q , istemperature
allowed T 1 , and the same thermal energy, q , is allowed
from the reservoir at T 2 to the reservoir at T 1 .
weight is allowed to fall, performing work, w , and the thermal energy produce
enters the reservoir.
3. The
e heat reservoir in the weight– heat reservoir system heat
is at thereservoir in the weight–
temperature T 1 . Theheat reservoir system is at the temperature T 1 . The
ight is allowed to fall, performing work, w , and theweight
thermal is allowed
energytoproduced,
fall, performing
q , work, w , and the thermal energy produced, q , Each of these processes is spontaneous and hence irreversible , and the
enters the reservoir.
process 3 can be considered as the sum of processes 1 and 2
ers the reservoir. degradation occurs in each of them. However, since process 3 is the sum of pro
1 and 2, the degradation occurring in process 3 must be greater than the de
of these processes is spontaneous and hence Each irreversible
of these processes
, and istherefore,
spontaneous and hence irreversible , and therefore, tion occurring in each of the processes 1 and 2. Thus, it can be said that pro
degradation occurs in
ion occurs in each of them. However, since process 3 is the sum of processes each of them. However, since process 3 is the sum of processes
is more irreversible than either process 1 or process 2. An examination of th
the degradation occurring in process 3 1must and 2,bethegreater
degradation
than occurring
the degrada- in process 3 must be greater than the degrada- processes indicates that both the amount of thermal energy transferred, q , a
temperatures between which this energy is transferred are important in defi
Degradation or dissipation of energy in the process 3 is higher compared to the
urring in each of the processes 1 and 2. tion
irreversible than either process 1 or process
occurring
Thus,
is more
2. An
it can be in each
irreversible
saidofthat
examination
the process
than either
processes31 and 2. Thus, it can be said that process
of the process
three1 or process 2. An examination of the three
3
quantitative scale of irreversibility. In the case of comparison between proces
degradation occurring in each of the processes 1 and 2
s indicates that both the amount of thermal processes
energy indicates that bothqthe
transferred, , and amount
the of thermal energy transferred, q , and with
process 3, the quantity q / T2 is smaller than the quantity q / T1 , which is in agre
the
the conclusion that process 1 is less irreversible than process 3. The q
temperatures between
tures between which this energy is transferred are important in defining a which this energy is transferred are important in defining q /aT can thus be taken as a measure of the degree of irreversibility of the p
tive scale of irreversibility. In the case of quantitative
comparison scale of irreversibility.
between process 1Inand the case of comparison between process 1 and and the value of q / T is the increase in entropy occurring as a result of th
INTRODUCTION TO THE THERMODYNAMICS
60 OF MATERIALS,
INTRODUCTION
2nd law of thermodynamics
SIXTH EDITION
TO THE THERMODYNAMICS OF MATERIALS, SIXTH EDITION
60 INTRODUCTION TO THE THERMODYNAMICS OF MATERIALS, SIXTH E

W
W W Temperature T1
Temperature T2 Temperature T2 Temperature T1

Figure 3.1 A weight– pulley– heat reservoir arrangement in which the work done by th
weight is degraded to thermal energy, which appears in the heat reservoi
1 Figure
A weight– pulley– heat reservoir arrangement 3.1 Athe
in which weight–
workpulley–
done heat reservoir
by the fallingarrangement in which the work done by the falling
Process 3 is said to be more irreversible or more spontaneous than either process1 or
weight is degraded to thermal energy, which appearsweight
in theisheat
degraded to thermal energy, which appears in the heat reservoir.
reservoir.
Lewis and Randall* considered the following three processes:
process 2
d Randall* considered the following three Lewis and Randall* considered the following three processes:
processes: 1. The heat reservoir in the weight– heat reservoir system is at the temperature T 2 .
weight is allowed to fall, performing work, w , and the thermal energy produce
1. The
e heat reservoir in the weight– heat reservoir system heat
is at thereservoir in the weight–
temperature enters the heat reservoir.
T 2 . Theheat reservoir system is at the temperature T 2 . The
ight is allowed to fall, performing work, w , and the thermal energy produced, q , work, w , and the thermal energy produced, q ,
weight is allowed to fall, performing 2. The heat reservoir at the temperature T 2 is placed in thermal contact with ano
An examination of the three processes indicates that both the amount of thermal
ers the heat reservoir. enters the heat reservoir. heat reservoir at a lower temperature T 1 , and the same thermal energy, q , is allo
to be transferred from the reservoir at T 2 to the reservoir at T 1 .
e heat reservoir at the temperature T 2 is placed 2.in The heat reservoir
thermal contact atwiththe another
temperature T 2 is placed in thermal contact with another
energy transferred, q, and the temperatures between which this energy is transferred
at reservoir at a lower temperature T 1 , and the sameheat reservoir
thermal at a lower
energy, q , istemperature
3. The heat reservoir in the weight– heat reservoir system is at the temperature T 1 .
allowed T 1 , and the same thermal energy, q , is allowed
weight is allowed to fall, performing work, w , and the thermal energy produce
to beattransferred
be transferred from the reservoir at T 2 to the reservoir T1. from the reservoir at T 2 to the reservoir at T 1 .
are important in defining a quantitative scale of irreversibility
3. The
e heat reservoir in the weight– heat reservoir system heat
is at thereservoir in the weight–
temperature
enters the reservoir.
T 1 . Theheat reservoir system is at the temperature T 1 . The
ight is allowed to fall, performing work, w , and theweight
thermal is allowed
energytoproduced,
fall, performing
q , work, w , and the thermal energy produced, q , Each of these processes is spontaneous and hence irreversible , and the
ers the reservoir. enters the reservoir. degradation occurs in each of them. However, since process 3 is the sum of pro
By comparing process 1 and process 3 we can say that, the quantity q /T2 is smaller
of these processes is spontaneous and hence Each irreversible
of these processes
, and istherefore,
spontaneous and hence irreversible , and therefore,
1 and 2, the degradation occurring in process 3 must be greater than the de
tion occurring in each of the processes 1 and 2. Thus, it can be said that pro
than the quantity q /T1 degradation occurs in
ion occurs in each of them. However, since process 3 is the sum of processes each of them. However, since process 3 is the sum of processes
is more irreversible than either process 1 or process 2. An examination of th
the degradation occurring in process 3 1must and 2,bethegreater
degradation
than occurring
the degrada- in process 3 must be greater than the degrada- processes indicates that both the amount of thermal energy transferred, q , a
temperatures between which this energy is transferred are important in defi
urring in each of the processes 1 and 2. tion occurring
Thus, it can be in each
saidofthat the process
processes31 and 2. Thus, it can be said that process 3
is more irreversible than either process quantitative scale of irreversibility. In the case of comparison between proces
irreversible than either process 1 or process 2. An examination of the three1 or process 2. An examination of the three
process 3, the quantity q / T2 is smaller than the quantity q / T1 , which is in agre
This is in agreement with the conclusion that process 1 is less irreversible than process 3.
s indicates that both the amount of thermal processes
energy indicates that bothqthe
transferred, , and amount
the of thermal energy transferred, q , and with the
the conclusion that process 1 is less irreversible than process 3. The q
temperatures between
tures between which this energy is transferred are important in defining a which this energy is transferred are important in defining q /aT can thus be taken as a measure of the degree of irreversibility of the p
tive scale of irreversibility. In the case of quantitative
comparison scale of irreversibility.
between process 1Inand the case of comparison between process 1 and and the value of q / T is the increase in entropy occurring as a result of th
INTRODUCTION TO THE THERMODYNAMICS
60 OF MATERIALS,
INTRODUCTION
2nd law of thermodynamics
SIXTH EDITION
TO THE THERMODYNAMICS OF MATERIALS, SIXTH EDITION
60 INTRODUCTION TO THE THERMODYNAMICS OF MATERIALS, SIXTH E

W
W W Temperature T1
Temperature T2 Temperature T2 Temperature T1

Figure 3.1 A weight– pulley– heat reservoir arrangement in which the work done by th

1 The quantity q/T can thus be taken as a measure of the degree of irreversibility of the
Figure
A weight– pulley– heat reservoir arrangement 3.1 Athe
in which weight–
workpulley–
done heat reservoir
by the fallingarrangement in which the work done by the falling
weight is degraded to thermal energy, which appears in the heat reservoi

weight is degraded to thermal energy, which appearsweight


in theisheat
degraded to thermal energy, which appears in the heat reservoir.
reservoir.
process, and the value of q/T is the increase in entropy occurring as a result of the Lewis and Randall* considered the following three processes:

d Randall* process.
considered the following three Lewis and Randall considered the following three processes:
processes: *
1. The heat reservoir in the weight– heat reservoir system is at the temperature T . 2
weight is allowed to fall, performing work, w , and the thermal energy produce
1. The
e heat reservoir in the weight– heat reservoir system heat
is at thereservoir in the weight–
temperature enters the heat reservoir.
T 2 . Theheat reservoir system is at the temperature T 2 . The
ight is allowed to fall, performing work, w , and the thermal energy produced, q , work, w , and the thermal energy produced, q ,
weight is allowed to fall, performing 2. The heat reservoir at the temperature T 2 is placed in thermal contact with ano
enters the heat reservoir. heat reservoir at a lower temperature T 1 , and the same thermal energy, q , is allo
ers the heat reservoir.
Thus, when the weight–heat reservoir system undergoes a spontaneous process which
e heat reservoir at the temperature T 2 is placed 2.in The heat reservoir
thermal contact atwiththe another
to be transferred from the reservoir at T 2 to the reservoir at T 1 .
temperature T 2 is placed in thermal contact with another
3. The heat reservoir in the weight– heat reservoir system is at the temperature T 1 .
at reservoir at a lower temperature T 1 , and the sameheat reservoir
thermal at a lower
energy, q , istemperature
allowed T 1 , and the same thermal energy, q , is allowed
weight is allowed to fall, performing work, w , and the thermal energy produce
causes the absorption of thermal energy q at the constant temperature T, we can
to beattransferred
be transferred from the reservoir at T 2 to the reservoir T1. from the reservoir at T 2 to the reservoir at T 1 . enters the reservoir.
3. The
e heat reservoir in the weight– heat reservoir system heat
is at thereservoir in the weight–
temperature T 1 . Theheat reservoir system is at the temperature T 1 . The
define a quantity produced by the system, lets say for now denoted as ΔS is given by
ight is allowed to fall, performing work, w , and theweight
thermal is allowed
energytoproduced,
fall, performing
q , work, w , and the thermal energy produced, q , Each of these processes is spontaneous and hence irreversible , and the
ers the reservoir. enters the reservoir. degradation occurs in each of them. However, since process 3 is the sum of pro
ΔS=q/T 1 and 2, the degradation occurring in process 3 must be greater than the de
of these processes is spontaneous and hence Each irreversible
of these processes
, and istherefore,
spontaneous and hence irreversible , and therefore, tion occurring in each of the processes 1 and 2. Thus, it can be said that pro
degradation occurs in
ion occurs in each of them. However, since process 3 is the sum of processes each of them. However, since process 3 is the sum of processes
is more irreversible than either process 1 or process 2. An examination of th
This value is larger in the case of the lower-temperature reservoir. The increase in the
the degradation occurring in process 3 1must and 2,bethegreater
degradation
than occurring
the degrada- in process 3 must be greater than the degrada- processes indicates that both the amount of thermal energy transferred, q , a
temperatures between which this energy is transferred are important in defi
urring in each of the processes 1 and 2. tion occurring
Thus, it can be in each
saidofthat the process
processes31 and 2. Thus, it can be said that process 3
quantity q/T caused by the process is thus a measure of the degree of irreversibility of
irreversible than either process 1 or process is more
2. An irreversible
examinationthan either
of the process
three1 or process 2. An examination of the three
quantitative scale of irreversibility. In the case of comparison between proces
process 3, the quantity q / T2 is smaller than the quantity q / T1 , which is in agre
the process.
s indicates that both the amount of thermal processes
energy
temperatures
indicates
between
that bothqthe
transferred,
which
, and
this
amount
the of thermal energy transferred, q , and with
energy is transferred are important in defining
the
the conclusion that process 1 is less irreversible than process 3. The q
tures between which this energy is transferred are important in defining a q /aT can thus be taken as a measure of the degree of irreversibility of the p
tive scale of irreversibility. In the case of quantitative
comparison scale of irreversibility.
between process 1Inand the case of comparison between process 1 and and the value of q / T is the increase in entropy occurring as a result of th
43
2nd law of thermodynamics
MATHEMATICAL INTERLUDE III: PFAFFIAN DIFFERENTIAL FORMS

Note: It is obvious that two (reversible) adiabats cannot intersect. Once Carathéo-
dory’s Principle is accepted, the concept of entropy can be defined without recourse
toCaratheodary formulation of 2 law
nd
Carnot cycles by using mathematical properties of certain linear differential
equations called Pfaffian expressions, summarized in the following mathematical
interlude.
Avoids the use of cycles and heat engines
MATHEMATICAL INTERLUDE III: PFAFFIAN DIFFERENTIAL FORMS 43
Uses mathematical terms and axioms to develop 2nd law of thermodynamics
4.6
Note: MATHEMATICAL
It is obvious that two INTERLUDE III: PFAFFIAN
(reversible) adiabats cannot intersect. Once Carathéo-
DIFFERENTIAL
dory’s Principle isFORMS
accepted, the concept of entropy can be defined without recourse
to Carnot cycles by using mathematical properties of certain linear differential
Caratheodary
A differential
equations called Theorem
expression
Pfaffian of the form summarized in the following mathematical
expressions,
Ifinterlude.
a Pfaffian expression
dL ¼ !i Xi dxi ð4-24Þ
has the property for which, in the neighborhood of any point P, there are points that
where Xi isbea connected
4.6cannot function oftoINTERLUDE
MATHEMATICAL the variables
P along xIII:
curves 2 ; . . satisfy
1 , xthat
PFAFFIAN. ; xr , isthe
called a Pfaffian
equation dL = 0, then the
differential
Pfaffian form.
DIFFERENTIAL The
expression equation
FORMShas an integrating factor
dL ¼ !i Xi dxi ¼ 0 ð4-25Þ
A differential expression
A differential of theofform
expression the form
is called Pfaffian differential equation. The differential forms are sometimes
dL ¼ ! X dx ð4-24Þ
exact, although generally they are not.i i i
We consider
where X is a three special
function of cases.
the variables x2 ; x2,…xn,
x1 ,x1, . . . ; xr , isiscalled
where Xi is a function of the
i variables calledaaPfaffian
Pfaffian differential form
differential form. The equation
1) dL is exact. Then
4.6 MATHEMATICAL INTERLUDE III: PFAFFIAN
nd
DIFFERENTIAL FORMS 2 law of thermodynamics
A differential expression of the form
If a Pfaffian expression
dL ¼ !i Xi dxi ð4-24Þ
has the property for which, in the neighborhood of any point P, there are points that
where Xi isbea connected
cannot function oftothe variables
P along curves 2 ; . . satisfy
x1 , xthat . ; xr , isthe
called a Pfaffian
equation dL = 0, then the
differential form. The equation
Pfaffian expression has an integrating factor
dL ¼ !i Xi dxi ¼ 0 ð4-25Þ
From the Caratheodary theorem the following conclusions can be drawn
is called Pfaffian differential equation. The differential forms are sometimes
exact, although
(a) the generally
existence of anthey are not. denominator for the differential expression for a
integrating
We considerheat
reversible three specialthat
transfer cases.
transformed the inexact differential into an exact
differential, and thereby providing an operational definition for some state function
1) dL is exact. Then
(b) the general tendency of this state function to increase.
qXi =qxj ¼ qXj qxi for all i; j ¼ 1; 2; . . . ; r ð4-26Þ

2) dL in not exact, but has an integrating factor.


This conclusion, which is another way of stating the Second Law, is known as the
An integrating
Caratheodory factor, "(x
principle. 1 , . .be
It can . ,xrstated
), is a as
factor that turns the inexact
differential
In the dL intoofanevery
neighborhood exactequilibrium
one, which statewe represent as ds. Writingsystem, there exist
of a thermodynamic
states unattainable from it by any adiabatic process (reversible or irreversible).
"dL ¼ ds ¼ !i ð"Xi Þ dxi ¼ !i ðqs=qxi Þj6¼i dxi ð4-27Þ
some examples involving only two variables. These do not provide the
generality we must have to treat thermodynamic systems of three or more

2nd law of thermodynamics

<.,-i
variables, but will provide concrete illustrations of the general behavior we will

~...
m-"

E"
-H

(:h
m"
,..,.

lm
lm
lm

9
9
o
r
invoke in the development.

=.

c~
9

=.

c~

~.~"
9

=,.t~ .0
In Chapter 1, we wrote the two-dimensional Pfaffian differential 6Z as

~.~"
=,.t~ .0
~ .-.

.-.
o

~.:~
"
~,~. ~ o
o~.~
=~

~ o
~o--~

~,~.

~
~
~

~.~
=~
~o--~

~
~
6Z(X, Y)= M(X, Y) dX + N(X, Y) d Y (1.27)

1"~
~
ml

c~
:-

0
and saw as an example equation (1.47)
0

~
em

I
m-"
,H

66d UChemical
- dV+ dT and Applications (1.47)
ml

c~
:-
Thermodynamics: Principles
~1~

+
0

+
,

so that
in which the differential dU is related to changes in volume and temperature.
..a
em

~_.~
I
~

~~

~.~

~o

~
=
~
~

~ _ ~

RT
.~
~~

dT. (2.43)

--"
d Vm +

II c~ - .
(Sqrev --

~
"
m-"
,H

Vm aT "m
lm

~
"~ o

~.c~
C~"
~~
lm
II
o

0
Applying the condition for exactness gives"
~.~ m

~"
g
B ,... ~

~ ~'~
⎛ ⎛ RT ⎞ ⎞
=-
-'.

b~ ~ ~'~& b~ - ' ~

9
⎜ ∂⎜
~g
⎟⎟ ⎛ ∂ ⎛ ∂U m ⎞ ⎞ ⎛ ∂ ⎛ ∂U m ⎞ ⎞
9 ~

⎜ ⎝ Vm ⎠ ⎟ = R
~1~

~'T
+
⎟ ⎟ = ⎜⎜ ⎜ ⎟ ⎟⎟ = 0
~. ~" F ~

⎜ ⎜
+

~
⎜ ∂T ⎟
~9%

Vm
o=o

~" = ' a

⎝ ∂Vm ⎝ ∂T ⎠Vm ⎠T ⎝ ∂T ⎝ ∂Vm ⎠T ⎠Vm


R:D

.~ .

⎜ ⎟
"~

⎝ ⎠Vm R
~

Because the two derivatives


OT are not equal, the differential expression for dqrev is inexact.
~1 ~

Vm
..a

~
~
4.6 MATHEMATICAL INTERLUDE III: PFAFFIAN
DIFFERENTIAL FORMS
2nd law of thermodynamics
A differential expression of the form
If a Pfaffian expression
dL ¼ !i Xi dxi ð4-24Þ
has the property for which, in the neighborhood of any point P, there are points that
where Xi isbea connected
cannot function oftothe variables
P along curves 2 ; . . satisfy
x1 , xthat . ; xr , isthe
called a Pfaffian
equation dL = 0, then the
differential
Pfaffian form. The equation
expression has an integrating factor
dL ¼ !i Xi dxi ¼ 0 ð4-25Þ
Mathematically, it can be shown that a two-dimensional Pfaffian is either exact, or, if it is
is called
inexact,Pfaffian differential
an integrating equation. The
denominator candifferential
always beforms aretosometimes
found convert it into a new, exact,
exact, although generally they are not.
differential.
We consider three special cases.

1) dL is exact. Then
Caratheodory showed that expressions for dqrev fall into the class of inexact but
integrable differential
qXi =qxj ¼expressions.
qXj qxi for That all i; jis,¼an integrating
1; 2; ...;r denominator
ð4-26Þ exists that can
convert the inexact differential into an exact differential.
2) dL in not exact, but has an integrating factor.
An integrating factor, "(x1 , . . . ,xr ), is a factor that turns the inexact
differential dL into an exact one, which we represent as ds. Writing

"dL ¼ ds ¼ !i ð"Xi Þ dxi ¼ !i ðqs=qxi Þj6¼i dxi ð4-27Þ


2nd law of thermodynamics
According to the Caratheodory theorem, the existence of an integrating denominator
that creates an exact differential (state function) out of any inexact differential is tied to
the existence of points (specified by the values of their xi's) that cannot be reached
from a given point by an adiabatic path (a solution curve).

In the neighborhood of every equilibrium state of a thermodynamic system, there exist


states unattainable from it by any adiabatic process (reversible or irreversible)

From a given thermodynamic state of the system, there are states that cannot be
reached from the initial state by way of any adiabatic process.
2nd law of thermodynamics
Let us define the system as being characterized by an empirical temperature, θ and any
other number of variables, x1,x2, ….xn

Initially, we will change only two independent variables, θ and x1. The First and Second Laws of Thermodynamics 69

θ will behave in a way analogous to


temperature T, and the other variable,
xj, will be the analogue of pressure p.

We can represent states of the system by a set of


isotherms

Figure 2.11 Graph of empirical temperature 0 against x, a state variable such as


2nd law of thermodynamics
Lets take two isotherms, θ1 and θ2, with θ2 < θ1

Lets take State 1, which is defined by θ1 and x1, can be connected to states 1' and 1"
by a series of reversible isothermal processes The First and Second Laws of Thermodynamics 69

Heat is absorbed or evolved along a reversible


isothermal path, and we will assume that this flow
of heat is a continuous function of x1 along the
isotherms, with the absorption or liberation
depending upon the direction in which x1 is varied.

Lets say heat is liberated in going from 1 to 1', then increasing amount of heat is
liberated on going from 1 to states farther and farther removed from 1 such as 1".

If the direction of the process is switched and the system proceeds from 1" to
1' or on to 1, heat would be absorbed in increasing amounts.
Figure 2.11 Graph of empirical temperature 0 against x, a state variable such as
2nd law of thermodynamics
For each state identified on the θ1 isothermal as 1, 1', 1".... , let us draw paths
representing reversible adiabatic processes that intersect a second isotherm
at θ2. The First and Second Laws of Thermodynamics 69

The intersections of the reversible adiabatic paths


from states 1, 1' and 1" on θ1 with those on θ2 are
denoted by 2, 2' and 2", respectively.

Along the three paths, 1-2, 1'-2', and 1"-2", no heat is absorbed or liberated because
the processes that connect these points are defined to be adiabatic.

We wish to show that no points to the left of 2 on the isotherm θ2 are accessible from
point 1 via any adiabatic path, reversible orFigure
irreversible.
2.11 Graph of empirical temperature 0 against x, a state variable such as
pressure. (a) Reversible adiabatic paths (solid lines: 1 " ~ 2 " ; 1' ~ 2 ' ; and 1 ~ 2 )
connect states on two isothermal lines of a general thermodynamic system: An
irreversible adiabatic path (dotted line: 1 --~ 2') can be shown to be forbidden, while an
2nd law of thermodynamics
Suppose we assume that some adiabatic path does exist between 1 and 2'.

Consider the cycle 1- 2’-1’- 1. The First and Second Laws of Thermodynamics 69

The net heat associated with this cycle would be


that arising from the last step 1’ - 1

We have defined the direction 1' - 1 to correspond to


an absorption of heat, which we will call q1’-1

The net work W done in the cycle, is given by W= -q1’-1

Thus, for this process, w is negative (and therefore performed by the system), since q1’-1
is positive, having been absorbed from the reservoir.
Figure 2.11 Graph of empirical temperature 0 against x, a state variable such as
pressure. (a) Reversible adiabatic paths (solid lines: 1 " ~ 2 " ; 1' ~ 2 ' ; and 1 ~ 2 )
connect states on two isothermal lines of a general thermodynamic system: An
irreversible adiabatic path (dotted line: 1 --~ 2') can be shown to be forbidden, while an
2nd law of thermodynamics
Thus, for this process, w is negative (and therefore performed by the system), since q1’-1
is positive, having been absorbed from the reservoir.
The First and Second Laws of Thermodynamics 69

The net effect of this cycle, then, is to


completely convert heat absorbed at a high
temperature reservoir into work.

Complete conversion of heat to work is not


possible

Hence, points to the left of 2 cannot be reached from point 1 by way of any adiabatic
path.

Figure 2.11 Graph of empirical temperature 0 against x, a state variable such as


pressure. (a) Reversible adiabatic paths (solid lines: 1 " ~ 2 " ; 1' ~ 2 ' ; and 1 ~ 2 )
connect states on two isothermal lines of a general thermodynamic system: An
irreversible adiabatic path (dotted line: 1 --~ 2') can be shown to be forbidden, while an
2nd law of thermodynamics
What about points to the right of 2? Can they be reached?

Consider an adiabatic path from point 1 to point 2a that is also located onandthe
The First isothermal
Second Laws of Thermodynamics 69
θ2.

The cycle of interest is 1-2a-2-1

Again, two of the three steps are adiabatic.

In this case, heat is evolved during the 2a - 2 step from the conversion of work into
heat.

The complete conversion of work into heat is not forbidden by the laws of
thermodynamics.

Thus, there are states to the right of 2 on the isotherm θ2of that
Figure 2.11 Graph are
empirical accessible
temperature from
0 against x, a state variable such as
pressure. (a) Reversible adiabatic paths (solid lines: 1 " ~ 2 " ; 1' ~ 2 ' ; and 1 ~ 2 )
1 via an adiabatic path. connect states on two isothermal lines of a general thermodynamic system: An
irreversible adiabatic path (dotted line: 1 --~ 2') can be shown to be forbidden, while an
2nd law of thermodynamics
Since the only constraint we have placed on θ2 is that it be less than θ1, the
second isotherm can be as arbitrarily close to the first as we wish.

There are states located in the plane defined by θ and x1 that are inaccessible from
Figure 2.11 Graph of empirical temperature 0 against x, a state variable such as
state 1. (a) Reversible adiabatic paths (solid lines: 1 " ~ 2 " ; 1' ~ 2 ' ; and 1 ~ 2 )
pressure.
connect states on two isothermal lines of a general thermodynamic system: An
irreversible adiabatic path (dotted line: 1 --~ 2') can be shown to be forbidden, while an
There is aadiabatic
irreversible sense of pathdirection to the
(dashed line: 1 ~ location of the
2a) is allowed. (b) inaccessible states.
A reversible adiabatic
path through state 1 at temperature 01 divides the states at lower temperatures into two
State 2, the
regions, thosestate reached
that are accessiblefrom 1 by a reversible
via irreversible adiabatic
adiabatic paths and those path,
that arerepresents
the division
not.
between the states on the second isotherm that are accessible and inaccessible from
state
heat 1.
is liberated in going from 1 to 1', then increasing a m o u n t s of heat are
same state 1 as earlier. The value of x2 in state 1 will fix the location of this state
on the isotherm in the new direction. A reversible adiabatic path can be
2nd law of thermodynamics
constructed that connects state 1 with a state on the second isothermal in the x2
direction. Irreversible states located on one side of this point will be inaccessible
from state
Within the neighborhood 1 by adiabatic
of every paths,
state in this while states located
thermodynamic system,onthere
the are
otherstates
side of that
point will
that cannot be reached be accessible.
via adiabatic Thus, there exist states located on the plane defined by 0
paths.
and x2 that are inaccessible from point 1. Similar conclusions can be drawn by
considering isotherms localized on the planes formed by 0 and each of the xi.
Thus, we can conclude that, within the neighborhood of every state in this
Given the existence of these states, then, the existence of an integrating denominator
thermodynamic system, there are states that cannot be reached via adiabatic
for the differential element of reversible heat, dqrev, is guaranteed from Caratheodory's
paths. Given the existence of these states, then, the existence of an integrating
theorem.
denominator for the differential element of reversible heat, ~Sqrev, is guaranteed
from Carath6odory's
66 Chemical theorem.
Thermodynamics: PrinciplesOur next task is to identify this integrating
and Applications
denominator.
dqrev for an ideal gas undergoing only pressure-volume work is an inexact differential.
so that
2.2f The Identification of the Absolute (Ideal Gas) Temperature
RT
as(Sqrev
the-- Integrating
d Vm + Denominator
dT. (2.43)
We have previously Vm showna Tthat "mthe Pfaff differential ~Sq~v for an ideal gas
undergoing only pressure-volume work {equation (2.43)} is an inexact
Applying the
differential. It condition
is easy toforshow
exactness
that gives"
division of equation (2.43) by the absolute
We can easily show that division
temperature of above
T yields equation
an exact by the expression.
differential absolute temperature
The divisionT gives
yields an exact differential expression.
qrev R R
= ~ d Vm + - d T. (2.45)
T OTVm VmT aT
undergoing only pressure-volume work {equation (2.43)} is an inexact
differential. It is easy to show that division of equation (2.43) by the absolute
2nd law of thermodynamics
temperature T yields an exact differential expression. The division gives

qrev R
= ~ d Vm + - d T. (2.45)
T Vm T aT

Application of the condition


Application of the for exactness
condition for shows thatshows
exactness both derivatives equal zeroequal
that both derivatives
zero, so equation (2.45) must be exact. Thus, we have determined that when an
ideal⎛⎜ ∂gas
⎛ R ⎞is⎞ involved, T is an integrating denominator for ~Sqrev, and the right
⎜ ⎟⎟ ⎛ 1 ⎞⎛ ∂ ⎛ ∂U m ⎞ ⎞ ⎛ 1 ⎞⎛ ∂ ⎛ ∂U m ⎞ ⎞
hand⎜ side⎝ Vm ⎠ of
⎟ equation (2.45) ⎜is ⎟the
⎜ total
⎜ ⎟differential
⎟ = ⎜ ⎟⎜⎜ for ⎜ a⎟ state
⎟⎟ = 0function that we
=0 ⎝ T ⎠ ∂V
⎝ m ⎝ ∂T ⎠ ⎝ T ⎠ ∂T ∂V
⎜ ∂T ⎟ Vm ⎠T ⎝ ⎝ m ⎠T ⎠Vm
will represent as dS. cc
⎜ ⎟
What
⎝ we
⎠Vm must consider now is the generality of the result obtained for the
special case of the ideal gas. We define a new thermodynamic system that is the
When an ideal gas is involved, T is an integrating denominator for dqrev
cc We should remember that an integrating denominator for all inexact differential expressions in
two dimensions is guaranteed. Hence, its existence for the differential reversible heat element is
not unexpected.
Caratheodary has indeed shown that absolute temperature functions equally well as an
integrating factor not only the ideal gas but for the most complex systems also

dqrev/T is an exact differential that we will represent as dS

S is a state function and we call it as entropy


2nd law of thermodynamics
The Caratheodory treatment is grounded in the mathematical behavior of Pfaffian
differential expressions, and the observation that a differential element of heat for a
reversible process can be written in this form, where the dxi's represent state variables.

It is not generally possible to write such expressions for the differential element of heat
for irreversible processes, and therefore, an integrating denominator does not exist for
irreversible processes.

The ability to calculate entropy changes by the integration of dqrev/T is strictly limited
to reversible processes.

A comparable integration using (dqirr/T) between states connected by an irreversible


process would not yield an entropy change for the process.

Entropy is a state function, the changes associated with irreversible processes can still
be calculated if a reversible path, perhaps a purely hypothetical one, can be conceived
for which dqrev/T can be evaluated.
2nd law of thermodynamics
For reversible processes, dqrev is an inexact Pfaffian differential expression, and dS
is an exact one

As an inexact differential expression, equations of the form, dqrev = 0, cannot be


integrated to yield a general solution for a surface qrev = qrev(X1.... Xn).

But it is still possible to identify reversible adiabatic paths for which the equality dqrev = 0
is satisfied

Since dS is an exact differential, equations for dS = 0 can be integrated.

The integration yields a family of solution surfaces, S = S(x1,...xn)= constant.

Each solution surface contains a set of thermodynamic states for which the entropy is
constant
2nd law of thermodynamics
The solution surfaces cannot intersect. If they did, states located at the points of
intersection would have multiple values of entropy, and this would violate a fundamental
property of state functions The First and Second Laws of Thermodynam

A set of parallel, isentropic surfaces ordered so that S1 > S2


1 i

> S3. The solid curve marked (dqrev = 0) represents a r:v I

reversible adiabatic path that connects two states that lie on


"-..6q~,.~=0~ ~ ~ -
the entropy surface, S2

Each surface corresponds to a different value for the constant


Figure entropy.
2.12 A set of parallel, isentropic surfaces ordered so that S l > $2 > $3. Th
curve marked (Sqrev = 0 represents a reversible adiabatic path that connects two
that lie on the entropy surface, $2. The dashed curves marked ~Sqirr = 0 are irrev
paths that connect states on different entropy surfaces. Only one of these two pa
be allowed; the other will be forbidden.
dS = 0 for a reversible adiabatic process because dqrev = 0.
it is easy to see that dS = 0 for a reversible adiabatic process because ~ q r e
Two points which can be connected by a reversible adiabatic path must
Two points which can be connected by a reversible adiabatic path must lie on the same
the same entropy surface and a solution curve must lie wholly within a s
surface.
entropy surface and a solution curve must lie wholly within a solution surface.
The solution surfaces cannot intersect. If they did, states located
points of intersection would have multiple values of entropy, and this
violate a fundamental property of state functions. Thus, the surfaces
expected to be ordered monotonically, either systematically increasi
All points on the same surface can be connected by some solution curve (reversible
decreasing) as one proceeds in a given direction from surface to surface. F
adiabatic process). purposes, let us assume Sl > $2 > $3 in Figure 2.12.
Presumably all points on the same surface can be connected by
solution curve (reversible adiabatic process). However, states on surface
example, cannot be connected to states on either S~ or $3 by any rev
2nd law of thermodynamics
All points on the same surface can be connected by some solution curve (reversible
adiabatic process).
The First and Second Laws of Thermodynam

1 i

States on surface S2, cannot be connected to states on The First and Second Laws of Thermodynamics
r:v I
69

either S1 or S3 by any reversible adiabatic path.


"-..6q~,.~=0~ ~ ~ -

Figure 2.12 A set of parallel, isentropic surfaces ordered so that $2 > $3. Th
Sl >

We have shown previously that for any given initial state there are states that are
curve marked (Sqrev = 0 represents a reversible adiabatic path that connects two
that lie on the entropy surface, $2. The dashed curves marked ~Sqirr = 0 are irrev
accessible via adiabatic paths from the initial state, as well as states that are
paths that connect states on different entropy surfaces. Only one of these two pa
be allowed; the other will be forbidden.
inaccessible from that initial state by way of adiabatic paths.
it is easy to see that dS = 0 for a reversible adiabatic process because ~ q r e
Two points which can be connected by a reversible adiabatic path must
the same entropy surface and a solution curve must lie wholly within a s
A reversible adiabatic path containing the initial state
surface.
The solution surfaces cannot intersect. If they did, states located
marked the division between the states that were points of intersection would have multiple values of entropy, and this

accessible or inaccessible from that state, with all violate a fundamental property of state functions. Thus, the surfaces
expected to be ordered monotonically, either systematically increasi
accessible states lying on one side of the reversible decreasing) as one proceeds in a given direction from surface to surface. F
purposes, let us assume Sl > $2 > $3 in Figure 2.12.
adiabatic path, and all inaccessible states lying on the Presumably all points on the same surface can be connected by
other side of it. solution curve (reversible adiabatic process). However, states on surface
example, cannot be connected to states on either S~ or $3 by any rev
2nd law of thermodynamics
In terms of the surfaces, the entropy surface on which an initial state resides
represents a division between accessible and inaccessible entropy surfaces.
The First and Second Laws of Thermodynamics 79

States that could be reached on one side


1 i

of the surface can be accessed by way of r:v I

irreversible adiabatic processes. "-..6q~,.~=0~ ~ ~ -

Figure 2.12 A set of parallel, isentropic surfaces ordered so that $2 > $3. The solid
Sl >
curve marked (Sqrev = 0 represents a reversible adiabatic path that connects two states
that lie on the entropy surface, $2. The dashed curves marked ~Sqirr = 0 are irreversible
All allowed irreversible adiabatic processes must go to surfaces with either consistently
paths that connect states on different entropy surfaces. Only one of these two paths will
be allowed; the other will be forbidden.
higher or consistently lower entropy.
it is easy to see that dS = 0 for a reversible adiabatic process because ~ q r e v = 0.
Two points which can be connected by a reversible adiabatic path must lie on
the same entropy surface and a solution curve must lie wholly within a solution
surface.
The solution surfaces cannot intersect. If they did, states located at the
Depending on the sign convention that we adopt for heat and temperature, one side
points of intersection would have multiple values of entropy, and this would
violate a fundamental property of state functions. Thus, the surfaces can be
will be accessible by spontaneous/irreversible adiabatic path
expected to be ordered monotonically, either systematically increasing (or
decreasing) as one proceeds in a given direction from surface to surface. For our
purposes, let us assume Sl > $2 > $3 in Figure 2.12.
Presumably all points on the same surface can be connected by some
solution curve (reversible adiabatic process). However, states on surface $2, for
2nd law of thermodynamics
The Caratheodory analysis has shown that the allowed entropy changes in
spontaneous/ irreversible adiabatic processes can occur in only one direction.

Lets choose a simple case to evaluate the direction of the inequality.

Let us consider two thermal reservoirs maintained at temperatures T1 and T2,


respectively, with T2 > T1

The reservoirs are in thermal contact with each other through a large number of
intermediate temperature reservoirs, with the whole system thermally insulated

Reservoir Reservoir
at T1 at T2

Intermediate Reservoirs

The intermediate reservoirs are established so that the temperature of each differs from
that of its neighbors by increments small enough that heat transfer can be regarded as
taking place reversibly from intermediate reservoir to intermediate reservoir.
2nd law of thermodynamics
Reservoir Reservoir
at T1 at T2

Intermediate Reservoirs

The temperature difference between the outer reservoirs is a measurable one, heat will
flow spontaneously from the high-temperature reservoir through the intermediate
reservoirs to the low-temperature one

Let us call the amount of heat leaving the high-temperature reservoir q2.

It will pass into and out of each of the intermediate reservoirs, so that their net entropy
change is zero.

Given the convention that we have established for the sign of heat flow, we can state
that q2 < 0.

Because the overall system is isolated, q1, the heat flowing into the low- temperature
reservoir is given by q1 = -q2. This implies that q1>0
2nd law of thermodynamics
The First and Second Laws of Thermodynamics 81

Reservoir Reservoir
at T1 the entropy change for each reservoir. The result is at T2

ql
Intermediate The
Reservoirs
AS1 = and Second Laws of Thermodynamics
First 81
T1 The First and Second Laws of Thermodynamics 81
reservoir. TheTheresult
the entropy change for eachand First and
is Second Laws of Thermodynamics 81
Since the heat was transferred reversibly out of the high-temperature reservoir and into
the entropy ql change for each reservoir. The result is
the low-temperature reservoir,
the = wechange
entropy
AS1 mayforuse
each these q2
reservoir.
AS2 quantities
= ~ . The result is to calculate the entropy
T1 T2
change for each reservoir. qlql
and AS1 ==
AS1 We have previously shown with complete generality that the entropy of a
T1
T1 composite system is the sum of the entropies of its components, and so we can
q2 write that
and
AS2 = ~ .
and T2
q~ q2
q2 AS-- t
AS2 = ~ . shown with complete
We have previously T1 generality
T2 that the entropy of a
T2 sum of the entropies of its components, and so we can
composite system is the q2
write that AS2 = ~ . which can be simplified to
We have previously
T2 shown with complete generality that the entropy of a
composite system is the sum of the entropies of its components, and so we can
q~ q2 q~ q~
write
A S - -that t
We have T1 T2 previously shown with =complete
AS . . . .
T1 7"2
ql I 1
T~
1 generality
7"2
1. that the
entropy of a
composite system q~ q2is the sum of the entropies of its components, and so we can
which can be A S--
simplified t to
write that T1 T2 Since ql > 0, and 1 / T l > l / T 2 with ~ > T1, we conclude that AS for this
allowed, spontaneous process is greater than zero. Having obtained this result
Since q1 > 0, and 1/T1 >1/T2 with T2 > T1, we conclude that ΔS for this spontaneous
which q~ beq~simplified
can
AS . . . . = ql for to
q~ Iq2
1
the specific case, we can extend it to the general case, because our earlier
conclusion1 1 . that there is an allowed direction to spontaneous adiabatic processes
process is greater than zero. AT1S - - 7"2 t applies
T~ 7"2
to all thermodynamic systems.
T1
q~
AS . . . .
q~ T2
= qlTo 1summarize
Since ql > 0, and 1 / T l > l / T 2 I with 1 1>. T1, we conclude that AS for this
~7"2
T1 7"2 T~
allowed, spontaneous process is greater than zero. Having obtained this result
for which can case,
the specific be simplified
we can extend todS(reversible adiabatic processes)- 0
it to the general case, because our earlier
2nd law of thermodynamics
There is an allowed direction to spontaneous adiabatic processes which applies to all
thermodynamic systems.

dS(reversible adiabatic processes) = 0

dS(irreversible adiabatic processes) > 0.

When we apply these statements to the universe, the ultimate adiabatically


enclosed system
ΔS(universe) ≥ 0

This equation provides a way to determine whether a process is reversible, irreversible


and allowed, or irreversible and forbidden

This equation can be considered as the mathematical formulation of 2nd law of


thermodynamics
2nd law of thermodynamics
When the net entropy change is zero, the process is reversible, and the system is said
to be at equilibrium

If the total entropy is greater than zero, the process will occur. Such a process is often
referred to as a spontaneous or natural process. If the net entropy change is negative,
the process is unnatural and will not occur.

Thus, the Second Law provides an important method for


predicting the spontaneity or reversibility of a process.
MM209 - Thermodynamics
Instructor : Aswani Yella
43
2nd law of thermodynamics
MATHEMATICAL INTERLUDE III: PFAFFIAN DIFFERENTIAL FORMS

Note: It is obvious that two (reversible) adiabats cannot intersect. Once Carathéo-
dory’s Principle is accepted, the concept of entropy can be defined without recourse
toCaratheodary formulation of 2 law
nd
Carnot cycles by using mathematical properties of certain linear differential
equations called Pfaffian expressions, summarized in the following mathematical
interlude.
Avoids the use of cycles and heat engines
MATHEMATICAL INTERLUDE III: PFAFFIAN DIFFERENTIAL FORMS 43
Uses mathematical terms and axioms to develop 2nd law of thermodynamics
4.6
Note: MATHEMATICAL
It is obvious that two INTERLUDE III: PFAFFIAN
(reversible) adiabats cannot intersect. Once Carathéo-
DIFFERENTIAL
dory’s Principle isFORMS
accepted, the concept of entropy can be defined without recourse
to Carnot cycles by using mathematical properties of certain linear differential
Caratheodary
A differential
equations called Theorem
expression
Pfaffian of the form summarized in the following mathematical
expressions,
Ifinterlude.
a Pfaffian expression
dL ¼ !i Xi dxi ð4-24Þ
has the property for which, in the neighborhood of any point P, there are points that
where Xi isbea connected
4.6cannot function oftoINTERLUDE
MATHEMATICAL the variables
P along xIII:
curves 2 ; . . satisfy
1 , xthat
PFAFFIAN. ; xr , isthe
called a Pfaffian
equation dL = 0, then the
differential
Pfaffian form.
DIFFERENTIAL The
expression equation
FORMShas an integrating factor
dL ¼ !i Xi dxi ¼ 0 ð4-25Þ
A differential expression
A differential of theofform
expression the form
is called Pfaffian differential equation. The differential forms are sometimes
dL ¼ ! X dx ð4-24Þ
exact, although generally they are not.i i i
We consider
where X is a three special
function of cases.
the variables x2 ; x2,…xn,
x1 ,x1, . . . ; xr , isiscalled
where Xi is a function of the
i variables calledaaPfaffian
Pfaffian differential form
differential form. The equation
1) dL is exact. Then
4.6 MATHEMATICAL INTERLUDE III: PFAFFIAN
nd
DIFFERENTIAL FORMS 2 law of thermodynamics
A differential expression of the form
If a Pfaffian expression
dL ¼ !i Xi dxi ð4-24Þ
has the property for which, in the neighborhood of any point P, there are points that
where Xi isbea connected
cannot function oftothe variables
P along curves 2 ; . . satisfy
x1 , xthat . ; xr , isthe
called a Pfaffian
equation dL = 0, then the
differential form. The equation
Pfaffian expression has an integrating factor
dL ¼ !i Xi dxi ¼ 0 ð4-25Þ
From the Caratheodary theorem the following conclusions can be drawn
is called Pfaffian differential equation. The differential forms are sometimes
exact, although
(a) the generally
existence of anthey are not. denominator for the differential expression for a
integrating
We considerheat
reversible three specialthat
transfer cases.
transformed the inexact differential into an exact
differential, and thereby providing an operational definition for some state function
1) dL is exact. Then
(b) the general tendency of this state function to increase.
qXi =qxj ¼ qXj qxi for all i; j ¼ 1; 2; . . . ; r ð4-26Þ

2) dL in not exact, but has an integrating factor.


This conclusion, which is another way of stating the Second Law, is known as the
An integrating
Caratheodory factor, "(x
principle. 1 , . .be
It can . ,xrstated
), is a as
factor that turns the inexact
differential
In the dL intoofanevery
neighborhood exactequilibrium
one, which statewe represent as ds. Writingsystem, there exist
of a thermodynamic
states unattainable from it by any adiabatic process (reversible or irreversible).
"dL ¼ ds ¼ !i ð"Xi Þ dxi ¼ !i ðqs=qxi Þj6¼i dxi ð4-27Þ
4.6 MATHEMATICAL INTERLUDE III: PFAFFIAN
DIFFERENTIAL FORMS
2nd law of thermodynamics
A differential expression of the form
If a Pfaffian expression
dL ¼ !i Xi dxi ð4-24Þ
has the property for which, in the neighborhood of any point P, there are points that
where Xi isbea connected
cannot function oftothe variables
P along curves 2 ; . . satisfy
x1 , xthat . ; xr , isthe
called a Pfaffian
equation dL = 0, then the
differential
Pfaffian form. The equation
expression has an integrating factor
dL ¼ !i Xi dxi ¼ 0 ð4-25Þ
Mathematically, it can be shown that a two-dimensional Pfaffian is either exact, or, if it is
is called
inexact,Pfaffian differential
an integrating equation. The
denominator candifferential
always beforms aretosometimes
found convert it into a new, exact,
exact, although generally they are not.
differential.
We consider three special cases.

1) dL is exact. Then
Caratheodory showed that expressions for dqrev fall into the class of inexact but
integrable differential
qXi =qxj ¼expressions.
qXj qxi for That all i; jis,¼an integrating
1; 2; ...;r denominator
ð4-26Þ exists that can
convert the inexact differential into an exact differential.
2) dL in not exact, but has an integrating factor.
An integrating factor, "(x1 , . . . ,xr ), is a factor that turns the inexact
differential dL into an exact one, which we represent as ds. Writing

"dL ¼ ds ¼ !i ð"Xi Þ dxi ¼ !i ðqs=qxi Þj6¼i dxi ð4-27Þ


some examples involving only two variables. These do not provide the
generality we must have to treat thermodynamic systems of three or more

2nd law of thermodynamics

<.,-i
variables, but will provide concrete illustrations of the general behavior we will

~...
m-"

E"
-H

(:h
m"
,..,.

lm
lm
lm

9
9
o
r
invoke in the development.

=.

c~
9

=.

c~

~.~"
9

=,.t~ .0
In Chapter 1, we wrote the two-dimensional Pfaffian differential 6Z as

~.~"
=,.t~ .0
~ .-.

.-.
o

~.:~
"
~,~. ~ o
o~.~
=~

~ o
~o--~

~,~.

~
~
~

~.~
=~
~o--~

~
~
6Z(X, Y)= M(X, Y) dX + N(X, Y) d Y (1.27)

1"~
~
ml

c~
:-

0
and saw as an example equation (1.47)
0

~
em

I
m-"
,H

66d UChemical
- dV+ dT and Applications (1.47)
ml

c~
:-
Thermodynamics: Principles
~1~

+
0

+
,

so that
in which the differential dU is related to changes in volume and temperature.
..a
em

~_.~
I
~

~~

~.~

~o

~
=
~
~

~ _ ~

RT
.~
~~

dT. (2.43)

--"
d Vm +

II c~ - .
(Sqrev --

~
"
m-"
,H

Vm aT "m
lm

~
"~ o

~.c~
C~"
~~
lm
II
o

0
Applying the condition for exactness gives"
~.~ m

~"
g
B ,... ~

~ ~'~
⎛ ⎛ RT ⎞ ⎞
=-
-'.

b~ ~ ~'~& b~ - ' ~

9
⎜ ∂⎜
~g
⎟⎟ ⎛ ∂ ⎛ ∂U m ⎞ ⎞ ⎛ ∂ ⎛ ∂U m ⎞ ⎞
9 ~

⎜ ⎝ Vm ⎠ ⎟ = R
~1~

~'T
+
⎟ ⎟ = ⎜⎜ ⎜ ⎟ ⎟⎟ = 0
~. ~" F ~

⎜ ⎜
+

~
⎜ ∂T ⎟
~9%

Vm
o=o

~" = ' a

⎝ ∂Vm ⎝ ∂T ⎠Vm ⎠T ⎝ ∂T ⎝ ∂Vm ⎠T ⎠Vm


R:D

.~ .

⎜ ⎟
"~

⎝ ⎠Vm R
~

Because the two derivatives


OT are not equal, the differential expression for dqrev is inexact.
~1 ~

Vm
..a

~
~
2nd law of thermodynamics
According to the Caratheodory theorem, the existence of an integrating denominator
that creates an exact differential (state function) out of any inexact differential is tied to
the existence of points (specified by the values of their xi's) that cannot be reached
from a given point by an adiabatic path (a solution curve).

In the neighborhood of every equilibrium state of a thermodynamic system, there exist


states unattainable from it by any adiabatic process (reversible or irreversible)

From a given thermodynamic state of the system, there are states that cannot be
reached from the initial state by way of any adiabatic process.
2nd law of thermodynamics
Let us define the system as being characterized by an empirical temperature, θ and any
other number of variables, x1,x2, ….xn

Initially, we will change only two independent variables, θ and x1. The First and Second Laws of Thermodynamics 69

θ will behave in a way analogous to


temperature T, and the other variable,
xj, will be the analogue of pressure p.

We can represent states of the system by a set of


isotherms

Figure 2.11 Graph of empirical temperature 0 against x, a state variable such as


2nd law of thermodynamics
Lets take two isotherms, θ1 and θ2, with θ2 < θ1

Lets take State 1, which is defined by θ1 and x1, can be connected to states 1' and 1"
by a series of reversible isothermal processes The First and Second Laws of Thermodynamics 69

Heat is absorbed or evolved along a reversible


isothermal path, and we will assume that this flow
of heat is a continuous function of x1 along the
isotherms, with the absorption or liberation
depending upon the direction in which x1 is varied.

Lets say heat is liberated in going from 1 to 1', then increasing amount of heat is
liberated on going from 1 to states farther and farther removed from 1 such as 1".

If the direction of the process is switched and the system proceeds from 1" to
1' or on to 1, heat would be absorbed in increasing amounts.
Figure 2.11 Graph of empirical temperature 0 against x, a state variable such as
2nd law of thermodynamics
For each state identified on the θ1 isothermal as 1, 1', 1".... , let us draw paths
representing reversible adiabatic processes that intersect a second isotherm
at θ2. The First and Second Laws of Thermodynamics 69

The intersections of the reversible adiabatic paths


from states 1, 1' and 1" on θ1 with those on θ2 are
denoted by 2, 2' and 2", respectively.

Along the three paths, 1-2, 1'-2', and 1"-2", no heat is absorbed or liberated because
the processes that connect these points are defined to be adiabatic.

We wish to show that no points to the left of 2 on the isotherm θ2 are accessible from
point 1 via any adiabatic path, reversible orFigure
irreversible.
2.11 Graph of empirical temperature 0 against x, a state variable such as
pressure. (a) Reversible adiabatic paths (solid lines: 1 " ~ 2 " ; 1' ~ 2 ' ; and 1 ~ 2 )
connect states on two isothermal lines of a general thermodynamic system: An
irreversible adiabatic path (dotted line: 1 --~ 2') can be shown to be forbidden, while an
2nd law of thermodynamics
Suppose we assume that some adiabatic path does exist between 1 and 2'.

Consider the cycle 1- 2’-1’- 1. The First and Second Laws of Thermodynamics 69

The net heat associated with this cycle would be


that arising from the last step 1’ - 1

We have defined the direction 1' - 1 to correspond to


an absorption of heat, which we will call q1’-1

The net work W done in the cycle, is given by W= -q1’-1

Thus, for this process, w is negative (and therefore performed by the system), since q1’-1
is positive, having been absorbed from the reservoir.
Figure 2.11 Graph of empirical temperature 0 against x, a state variable such as
pressure. (a) Reversible adiabatic paths (solid lines: 1 " ~ 2 " ; 1' ~ 2 ' ; and 1 ~ 2 )
connect states on two isothermal lines of a general thermodynamic system: An
irreversible adiabatic path (dotted line: 1 --~ 2') can be shown to be forbidden, while an
2nd law of thermodynamics
Thus, for this process, w is negative (and therefore performed by the system), since q1’-1
is positive, having been absorbed from the reservoir.
The First and Second Laws of Thermodynamics 69

The net effect of this cycle, then, is to


completely convert heat absorbed at a high
temperature reservoir into work.

Complete conversion of heat to work is not


possible

Hence, points to the left of 2 cannot be reached from point 1 by way of any adiabatic
path.

Figure 2.11 Graph of empirical temperature 0 against x, a state variable such as


pressure. (a) Reversible adiabatic paths (solid lines: 1 " ~ 2 " ; 1' ~ 2 ' ; and 1 ~ 2 )
connect states on two isothermal lines of a general thermodynamic system: An
irreversible adiabatic path (dotted line: 1 --~ 2') can be shown to be forbidden, while an
2nd law of thermodynamics
What about points to the right of 2? Can they be reached?

Consider an adiabatic path from point 1 to point 2a that is also located onandthe
The First isothermal
Second Laws of Thermodynamics 69
θ2.

The cycle of interest is 1-2a-2-1

Again, two of the three steps are adiabatic.

In this case, heat is evolved during the 2a - 2 step from the conversion of work into
heat.

The complete conversion of work into heat is not forbidden by the laws of
thermodynamics.

Thus, there are states to the right of 2 on the isotherm θ2of that
Figure 2.11 Graph are
empirical accessible
temperature from
0 against x, a state variable such as
pressure. (a) Reversible adiabatic paths (solid lines: 1 " ~ 2 " ; 1' ~ 2 ' ; and 1 ~ 2 )
1 via an adiabatic path. connect states on two isothermal lines of a general thermodynamic system: An
irreversible adiabatic path (dotted line: 1 --~ 2') can be shown to be forbidden, while an
2nd law of thermodynamics
Since the only constraint we have placed on θ2 is that it be less than θ1, the
second isotherm can be as arbitrarily close to the first as we wish.

There are states located in the plane defined by θ and x1 that are inaccessible from
Figure 2.11 Graph of empirical temperature 0 against x, a state variable such as
state 1. (a) Reversible adiabatic paths (solid lines: 1 " ~ 2 " ; 1' ~ 2 ' ; and 1 ~ 2 )
pressure.
connect states on two isothermal lines of a general thermodynamic system: An
irreversible adiabatic path (dotted line: 1 --~ 2') can be shown to be forbidden, while an
There is aadiabatic
irreversible sense of pathdirection to the
(dashed line: 1 ~ location of the
2a) is allowed. (b) inaccessible states.
A reversible adiabatic
path through state 1 at temperature 01 divides the states at lower temperatures into two
State 2, the
regions, thosestate reached
that are accessiblefrom 1 by a reversible
via irreversible adiabatic
adiabatic paths and those path,
that arerepresents
the division
not.
between the states on the second isotherm that are accessible and inaccessible from
state
heat 1.
is liberated in going from 1 to 1', then increasing a m o u n t s of heat are
same state 1 as earlier. The value of x2 in state 1 will fix the location of this state
on the isotherm in the new direction. A reversible adiabatic path can be
2nd law of thermodynamics
constructed that connects state 1 with a state on the second isothermal in the x2
direction. Irreversible states located on one side of this point will be inaccessible
from state
Within the neighborhood 1 by adiabatic
of every paths,
state in this while states located
thermodynamic system,onthere
the are
otherstates
side of that
point will
that cannot be reached be accessible.
via adiabatic Thus, there exist states located on the plane defined by 0
paths.
and x2 that are inaccessible from point 1. Similar conclusions can be drawn by
considering isotherms localized on the planes formed by 0 and each of the xi.
Thus, we can conclude that, within the neighborhood of every state in this
Given the existence of these states, then, the existence of an integrating denominator
thermodynamic system, there are states that cannot be reached via adiabatic
for the differential element of reversible heat, dqrev, is guaranteed from Caratheodory's
paths. Given the existence of these states, then, the existence of an integrating
theorem.
denominator for the differential element of reversible heat, ~Sqrev, is guaranteed
from Carath6odory's
66 Chemical theorem.
Thermodynamics: PrinciplesOur next task is to identify this integrating
and Applications
denominator.
dqrev for an ideal gas undergoing only pressure-volume work is an inexact differential.
so that
2.2f The Identification of the Absolute (Ideal Gas) Temperature
RT
as(Sqrev
the-- Integrating
d Vm + Denominator
dT. (2.43)
We have previously Vm showna Tthat "mthe Pfaff differential ~Sq~v for an ideal gas
undergoing only pressure-volume work {equation (2.43)} is an inexact
Applying the
differential. It condition
is easy toforshow
exactness
that gives"
division of equation (2.43) by the absolute
We can easily show that division
temperature of above
T yields equation
an exact by the expression.
differential absolute temperature
The divisionT gives
yields an exact differential expression.
qrev R R
= ~ d Vm + - d T. (2.45)
T OTVm VmT aT
undergoing only pressure-volume work {equation (2.43)} is an inexact
differential. It is easy to show that division of equation (2.43) by the absolute
2nd law of thermodynamics
temperature T yields an exact differential expression. The division gives

qrev R
= ~ d Vm + - d T. (2.45)
T Vm T aT

Application of the condition


Application of the for exactness
condition for shows thatshows
exactness both derivatives equal zeroequal
that both derivatives
zero, so equation (2.45) must be exact. Thus, we have determined that when an
ideal⎛⎜ ∂gas
⎛ R ⎞is⎞ involved, T is an integrating denominator for ~Sqrev, and the right
⎜ ⎟⎟ ⎛ 1 ⎞⎛ ∂ ⎛ ∂U m ⎞ ⎞ ⎛ 1 ⎞⎛ ∂ ⎛ ∂U m ⎞ ⎞
hand⎜ side⎝ Vm ⎠ of
⎟ equation (2.45) ⎜is ⎟the
⎜ total
⎜ ⎟differential
⎟ = ⎜ ⎟⎜⎜ for ⎜ a⎟ state
⎟⎟ = 0function that we
=0 ⎝ T ⎠ ∂V
⎝ m ⎝ ∂T ⎠ ⎝ T ⎠ ∂T ∂V
⎜ ∂T ⎟ Vm ⎠T ⎝ ⎝ m ⎠T ⎠Vm
will represent as dS. cc
⎜ ⎟
What
⎝ we
⎠Vm must consider now is the generality of the result obtained for the
special case of the ideal gas. We define a new thermodynamic system that is the
When an ideal gas is involved, T is an integrating denominator for dqrev
cc We should remember that an integrating denominator for all inexact differential expressions in
two dimensions is guaranteed. Hence, its existence for the differential reversible heat element is
not unexpected.
Caratheodary has indeed shown that absolute temperature functions equally well as an
integrating factor not only the ideal gas but for the most complex systems also

dqrev/T is an exact differential that we will represent as dS

S is a state function and we call it as entropy


2nd law of thermodynamics
The Caratheodory treatment is grounded in the mathematical behavior of Pfaffian
differential expressions, and the observation that a differential element of heat for a
reversible process can be written in this form, where the dxi's represent state variables.

It is not generally possible to write such expressions for the differential element of heat
for irreversible processes, and therefore, an integrating denominator does not exist for
irreversible processes.

The ability to calculate entropy changes by the integration of dqrev/T is strictly limited
to reversible processes.
2nd law of thermodynamics
For reversible processes, dqrev is an inexact Pfaffian differential expression, and dS
is an exact one

As an inexact differential expression, equations of the form, dqrev = 0, cannot be


integrated to yield a general solution for a surface qrev = qrev(X1.... Xn).

But it is still possible to identify reversible adiabatic paths for which the equality dqrev = 0
is satisfied

Since dS is an exact differential, equations for dS = 0 can be integrated.

The integration yields a family of solution surfaces, S = S(x1,...xn)= constant.

Each solution surface contains a set of thermodynamic states for which the entropy is
constant
2nd law of thermodynamics
The solution surfaces cannot intersect. If they did, states located at the points of
intersection would have multiple values of entropy, and this would violate a fundamental
property of state functions The First and Second Laws of Thermodynam

A set of parallel, isentropic surfaces ordered so that S1 > S2


1 i

> S3. The solid curve marked (dqrev = 0) represents a r:v I

reversible adiabatic path that connects two states that lie on


"-..6q~,.~=0~ ~ ~ -
the entropy surface, S2

Each surface corresponds to a different value for the constant


Figure entropy.
2.12 A set of parallel, isentropic surfaces ordered so that S l > $2 > $3. Th
curve marked (Sqrev = 0 represents a reversible adiabatic path that connects two
that lie on the entropy surface, $2. The dashed curves marked ~Sqirr = 0 are irrev
paths that connect states on different entropy surfaces. Only one of these two pa
be allowed; the other will be forbidden.
dS = 0 for a reversible adiabatic process because dqrev = 0.
it is easy to see that dS = 0 for a reversible adiabatic process because ~ q r e
Two points which can be connected by a reversible adiabatic path must
Two points which can be connected by a reversible adiabatic path must lie on the same
the same entropy surface and a solution curve must lie wholly within a s
surface.
entropy surface and a solution curve must lie wholly within a solution surface.
The solution surfaces cannot intersect. If they did, states located
points of intersection would have multiple values of entropy, and this
violate a fundamental property of state functions. Thus, the surfaces
expected to be ordered monotonically, either systematically increasi
All points on the same surface can be connected by some solution curve (reversible
decreasing) as one proceeds in a given direction from surface to surface. F
adiabatic process). purposes, let us assume Sl > $2 > $3 in Figure 2.12.
Presumably all points on the same surface can be connected by
solution curve (reversible adiabatic process). However, states on surface
example, cannot be connected to states on either S~ or $3 by any rev
2nd law of thermodynamics
All points on the same surface can be connected by some solution curve (reversible
adiabatic process).
The First and Second Laws of Thermodynam

1 i

States on surface S2, cannot be connected to states on The First and Second Laws of Thermodynamics
r:v I
69

either S1 or S3 by any reversible adiabatic path.


"-..6q~,.~=0~ ~ ~ -

Figure 2.12 A set of parallel, isentropic surfaces ordered so that $2 > $3. Th
Sl >

We have shown previously that for any given initial state there are states that are
curve marked (Sqrev = 0 represents a reversible adiabatic path that connects two
that lie on the entropy surface, $2. The dashed curves marked ~Sqirr = 0 are irrev
accessible via adiabatic paths from the initial state, as well as states that are
paths that connect states on different entropy surfaces. Only one of these two pa
be allowed; the other will be forbidden.
inaccessible from that initial state by way of adiabatic paths.
it is easy to see that dS = 0 for a reversible adiabatic process because ~ q r e
Two points which can be connected by a reversible adiabatic path must
the same entropy surface and a solution curve must lie wholly within a s
A reversible adiabatic path containing the initial state
surface.
The solution surfaces cannot intersect. If they did, states located
marked the division between the states that were points of intersection would have multiple values of entropy, and this

accessible or inaccessible from that state, with all violate a fundamental property of state functions. Thus, the surfaces
expected to be ordered monotonically, either systematically increasi
accessible states lying on one side of the reversible decreasing) as one proceeds in a given direction from surface to surface. F
purposes, let us assume Sl > $2 > $3 in Figure 2.12.
adiabatic path, and all inaccessible states lying on the Presumably all points on the same surface can be connected by
other side of it. solution curve (reversible adiabatic process). However, states on surface
example, cannot be connected to states on either S~ or $3 by any rev
2nd law of thermodynamics
In terms of the surfaces, the entropy surface on which an initial state resides
represents a division between accessible and inaccessible entropy surfaces.
The First and Second Laws of Thermodynamics 79

States that could be reached on one side


1 i

of the surface can be accessed by way of r:v I

irreversible adiabatic processes. "-..6q~,.~=0~ ~ ~ -

Figure 2.12 A set of parallel, isentropic surfaces ordered so that $2 > $3. The solid
Sl >
curve marked (Sqrev = 0 represents a reversible adiabatic path that connects two states
that lie on the entropy surface, $2. The dashed curves marked ~Sqirr = 0 are irreversible
All allowed irreversible adiabatic processes must go to surfaces with either consistently
paths that connect states on different entropy surfaces. Only one of these two paths will
be allowed; the other will be forbidden.
higher or consistently lower entropy.
it is easy to see that dS = 0 for a reversible adiabatic process because ~ q r e v = 0.
Two points which can be connected by a reversible adiabatic path must lie on
the same entropy surface and a solution curve must lie wholly within a solution
surface.
The solution surfaces cannot intersect. If they did, states located at the
Depending on the sign convention that we adopt for heat and temperature, one side
points of intersection would have multiple values of entropy, and this would
violate a fundamental property of state functions. Thus, the surfaces can be
will be accessible by spontaneous/irreversible adiabatic path
expected to be ordered monotonically, either systematically increasing (or
decreasing) as one proceeds in a given direction from surface to surface. For our
purposes, let us assume Sl > $2 > $3 in Figure 2.12.
Presumably all points on the same surface can be connected by some
solution curve (reversible adiabatic process). However, states on surface $2, for
2nd law of thermodynamics
The Caratheodory analysis has shown that the allowed entropy changes in
spontaneous/ irreversible adiabatic processes can occur in only one direction.

Lets choose a simple case to evaluate the direction of the inequality.

Let us consider two thermal reservoirs maintained at temperatures T1 and T2,


respectively, with T2 > T1

The reservoirs are in thermal contact with each other through a large number of
intermediate temperature reservoirs, with the whole system thermally insulated

Reservoir Reservoir
at T1 at T2

Intermediate Reservoirs

The intermediate reservoirs are established so that the temperature of each differs from
that of its neighbors by increments small enough that heat transfer can be regarded as
taking place reversibly from intermediate reservoir to intermediate reservoir.
2nd law of thermodynamics
Reservoir Reservoir
at T1 at T2

Intermediate Reservoirs

The temperature difference between the outer reservoirs is a measurable one, heat will
flow spontaneously from the high-temperature reservoir through the intermediate
reservoirs to the low-temperature one

Let us call the amount of heat leaving the high-temperature reservoir q2.

It will pass into and out of each of the intermediate reservoirs, so that their net entropy
change is zero.

Given the convention that we have established for the sign of heat flow, we can state
that q2 < 0.

Because the overall system is isolated, q1, the heat flowing into the low- temperature
reservoir is given by q1 = -q2. This implies that q1>0
2nd law of thermodynamics
The First and Second Laws of Thermodynamics 81

Reservoir Reservoir
at T1 the entropy change for each reservoir. The result is at T2

ql
Intermediate The
Reservoirs
AS1 = and Second Laws of Thermodynamics
First 81
T1 The First and Second Laws of Thermodynamics 81
reservoir. TheTheresult
the entropy change for eachand First and
is Second Laws of Thermodynamics 81
Since the heat was transferred reversibly out of the high-temperature reservoir and into
the entropy ql change for each reservoir. The result is
the low-temperature reservoir,
the = wechange
entropy
AS1 mayforuse
each these q2
reservoir.
AS2 quantities
= ~ . The result is to calculate the entropy
T1 T2
change for each reservoir. qlql
and AS1 ==
AS1 We have previously shown with complete generality that the entropy of a
T1
T1 composite system is the sum of the entropies of its components, and so we can
q2 write that
and
AS2 = ~ .
and T2
q~ q2
q2 AS-- t
AS2 = ~ . shown with complete
We have previously T1 generality
T2 that the entropy of a
T2 sum of the entropies of its components, and so we can
composite system is the q2
write that AS2 = ~ . which can be simplified to
We have previously
T2 shown with complete generality that the entropy of a
composite system is the sum of the entropies of its components, and so we can
q~ q2 q~ q~
write
A S - -that t
We have T1 T2 previously shown with =complete
AS . . . .
T1 7"2
ql I 1
T~
1 generality
7"2
1. that the
entropy of a
composite system q~ q2is the sum of the entropies of its components, and so we can
which can be A S--
simplified t to
write that T1 T2 Since ql > 0, and 1 / T l > l / T 2 with ~ > T1, we conclude that AS for this
allowed, spontaneous process is greater than zero. Having obtained this result
Since q1 > 0, and 1/T1 >1/T2 with T2 > T1, we conclude that ΔS for this spontaneous
which q~ beq~simplified
can
AS . . . . = ql for to
q~ Iq2
1
the specific case, we can extend it to the general case, because our earlier
conclusion1 1 . that there is an allowed direction to spontaneous adiabatic processes
process is greater than zero. AT1S - - 7"2 t applies
T~ 7"2
to all thermodynamic systems.
T1
q~
AS . . . .
q~ T2
= qlTo 1summarize
Since ql > 0, and 1 / T l > l / T 2 I with 1 1>. T1, we conclude that AS for this
~7"2
T1 7"2 T~
allowed, spontaneous process is greater than zero. Having obtained this result
for which can case,
the specific be simplified
we can extend todS(reversible adiabatic processes)- 0
it to the general case, because our earlier
2nd law of thermodynamics
There is an allowed direction to spontaneous adiabatic processes which applies to all
thermodynamic systems.

dS(reversible adiabatic processes) = 0

dS(irreversible adiabatic processes) > 0.

When we apply these statements to the universe, the ultimate adiabatically


enclosed system
ΔS(universe) ≥ 0

This equation provides a way to determine whether a process is reversible, irreversible


and allowed, or irreversible and forbidden

This equation can be considered as the mathematical formulation of 2nd law of


thermodynamics
2nd law of thermodynamics
When the net entropy change is zero, the process is reversible, and the system is said
to be at equilibrium

If the total entropy is greater than zero, the process will occur. Such a process is often
referred to as a spontaneous or natural process. If the net entropy change is negative,
the process is unnatural and will not occur.

Thus, the Second Law provides an important method for


predicting the spontaneity or reversibility of a process.
:AA…b\dA:
!d: \‡ p…A‡‡”…A
)™ YA !bg‡pYA…\2—\__ )A _g—A…8 p…A‡‡”…A
:AA…b\dA:!d: YA )™ YA !bg‡pYA…\2 p…A‡‡”…A !d: YA
Y\‡nd
g‡‡\)_A
—A\QY
YAd
Y! gJ:”…\dQ
:…gp3.5)A_g—
YA p\‡gdu
\‡ ”_\b!A
AN ILLUSTRATION \8 !d: 2 law of thermodynamics
A˜p!d‡\gd
 \‡ A–Ad pg‡‡\)_A
46 Introduction to the Thermodynamics of Materials
g–A…‡Ygg pg‡\\gd8
!JA… ‡gbA
OF IRREVERSIBLE
YA p\‡gd
YAd
Y!b!™
g‡2\__!\gd‡
:”…\dQ Y\‡ A˜p!d‡\gd YA p\‡gd b!™
46 Introduction to the Thermodynamics of Materials
:…gp3.5)A_g—
AND REVERSIBLE AN ILLUSTRATION \8 !d: !JA… ‡gbA
OF IRREVERSIBLE g‡2\__!\gd‡
AND REVERSIBLE
PROCESSES PROCESSES
rYAYA…
‡A_A :g—d Y\‡ILLUSTRATION
g
!2”!__™
\‡ Kd!_ Y!ppAd‡ OF REVERSIBLE
pg‡\\gdu ! Q\–Ad AND
\d rYAYA… Y\‡IRREVERSIBLE
2!‡A !2”!__™ Y!ppAd‡ PROCESSES
\d ! Q\–Ad 2!‡A
Consider a system of water and water vapor at the uniform temperature T contained Consider
in a a system of water and water vapor at the uniform temperature T contained in a
cylinder fitted with a frictionless piston, and let the cylinder be placed in thermal contact
cylinder
with afitted with a frictionless piston, and let the cylinder be placed in thermal contact with a
The permanent change in the external agency caused by the cyclic process carried out
heat reservoir which is also at the constant temperature T. This system is shown in heat
Fig.reservoir
3.2 which is also at the constant temperature T. This system is shown in Fig. 3.2

irreversibly is 2ΔPV.

  ‘u‘ YA p…A‡‡”…A \dFigure


Figure 3.2 A thermostalled piston and cylinder containing water and
YA3.2Q!‡ \d YA p\‡gd r!s \‡ :AA…b\dA: )™ YA —
A thermostalled piston and cylinder containing water and
water vapor.pg—:A… \d YA p!du J YA …!™ \‡ …Abg–A: water vapor. YA Q!‡ A˜p!d:‡ ‡”::Ad_™ !d: \……A–A…‡\)

The smaller the g value


!
The water vapor in the cylinder Kd!_ of
exerts a ‡!A
δP,r)suthen
certain pressure J the Q!‡
YA ,more
which nearly
A˜p!d:‡
The
equal are
the vapor ‡_g—_™8
iswater in the cylinder)™
the
…Abg–\dQ
exerts
two work gdA
a certain pressure
terms,
p!…\2_A and
, which isgJthein
_A!: pg—
the limit
saturated vapor that
pressurethey
of waterare
at theequal,
temperatureno permanent
T. The system is exactly change
saturated occurs
at vapor pressure of waterinat the external
the temperature agency,
T. The and
system is exactly at
YApressure
equilibrium when the external p…g2A‡‡ acting on\‡the…A–A…‡\)_A
piston, P , equals r2su
theequilibrium
ext
internal when the external pressure acting on the piston, P , equals the internal ext
hence the cyclic process
pressure acting on the piston,
has been conducted reversibly.
pressure acting on the piston,
, and when the temperature of the water+water , and when the temperature of the water+water
vapor in the cylinder equals the temperature T of the constant-temperature heat reservoir.
vapor in the cylinder equals the temperature T of the constant-temperature heat reservoir.
If the external pressure acting on the piston, Pext is suddenly decreased by a finiteIf amount
the external pressure acting on the piston, Pext is suddenly decreased by a finite amount
Thus, reversibly,
degradation, where is =process
whichqrev
if the evaporation U+was
given . If
is(q
max
the processreversibly,
conducted
–q)=(w is–w),
carried out irreversibly,
then
accounts heat
for q
the then less heat
leaves
fact that the
less qheat
heat is
Az”\_\)…\”b
is transferred —\Y \‡
from the reservoir to the‡”……g”d:\dQ‡u
rev
cylinder, where q= ‡
max
U+w.AbpA…!”…Arev —\__ )A Y! gJ \‡ ‡”……g”d:
The difference between
reservoir and enters
transferred the
to the cylinder
cylinder at thethe
from temperature
reservoir T. Theduring
during change
the in the entropy
irreversible process ofthan
the is
the work
!d:
transferred
heat reservoir is
done
\‡
during
given 2
during
the
by
nd law of thermodynamics
the reversible
p…A‡‡”…A
reversible
Eq. (3.1)
—\__
as
process
)A
process.
and that done
_g—A…8 :AA…b\dA:the irreversible
)™ YAprocess,
!bg‡pYA…\2 p…A‡‡”…A !d:
(wmax w), is the mechanical energy which has been degraded to thermal energy (heat) in
Thus,—A\QY gJ YA p\‡gdu
if the evaporation process is conducted
\‡ A–Adreversibly,
pg‡‡\)_A thenY!
heat :”…\dQ
q leavesY\‡ A˜p!d‡\gd YA p\‡gd
the heat
the cylinder as a result of the irreversible nature of the process.46This heatrev
Introduction produced by of Materials
to the Thermodynamics
g–A…‡Ygg
reservoir and enters
degradation, which is \‡
thegiven”_\b!A
cylinder
as (qrev the pg‡\\gd8
at–q)=(w
temperature
max
YAd
T. The
–w), accounts :…gp
forchange )A_g—
3.5in
the fact the
that
AN \8 is!d:
entropy
less heat
ILLUSTRATION the!JA… ‡gbA
of IRREVERSIBLE
OF g‡2\__!
AND REVERSIBLE
Consider only
heat reservoir the evaporation
is given by Eq. (3.1) asprocess PROCESSES
‡A_Ato :g—d
transferred g from
the cylinder \‡ Kd!_ pg‡\\gdu
the reservoir rYAYA…
during the irreversible Y\‡ process !2”!__™
than is Y!ppAd‡ \d ! Q\–Ad
transferred during the reversible process. Consider a system of water and water vapor at the uniform temperature T contained i
cylinder fitted with a frictionless piston, and let the cylinder be placed in thermal contact wi
Thus, if the evaporation process is conducted reversibly, then heat
heatreservoir leaves
qrev which theat heat
is also the constant temperature T. This system is shown in Fig.
If the evaporation process is conducted reversibly, then heat qrev leaves
reservoir and enters the cylinder at the temperature T. The change in the entropy of the
the heat
wherereservoir
the negative
andissign
heat reservoir enterscorresponds
given bythe
to heat leaving the heat reservoir, and thus the
Eq. cylinder
(3.1) as at the temperature T
entropy of the reservoir decreases. The change in the entropy of the water and water
vapor in the cylinder is
where the negative sign corresponds to heat leaving the heat reservoir, and thus the
entropy of the reservoir decreases. The change in the entropy of the water and water
vapor in the cylinder is
where the negative sign corresponds to heat leaving the heat reservoir, and thus the
where theentropy
positive signreservoir
of the corresponds to heat
decreases. The entering
change inthe
thecylinder, and
entropy of thethus theand
water entropy
water of
the contents
vaporofinthe
the cylinder
cylinder isincreases. The change in the entropy of the combined water-
vapor-heat reservoir system is thus
where the positive sign corresponds to heat entering the cylinder, and thus the entropy of
the contents of the cylinder increases. The change in the entropy of the combined water-
vapor-heat reservoir system is thus
where the positive sign corresponds to heat entering the cylinder, and thus the entropy of
This zero thechange
contentsinofentropy is due
the cylinder to the The
 
increases. fact
‘u‘thatYA
changethe
in process
p…A‡‡”…A
the was
entropy of\dcarried
theYA out \d
Q!‡
combined reversibly,
YA p\‡gd r!s \‡ :AA…b\dA:
water-
Figure 3.2 A thermostalled piston and cylinder containing water and
i.e., no degradation occurred
vapor-heat reservoir during
system the process.
ispg—:A…
thus \d YA p!du J YA …!™ \‡ …Abg–A: water vapor. YA Q!‡ A˜p!d:‡ ‡”::Ad_™ !d:
If the evaporation is carried out irreversibly then heat q (q<qrev) is transferred from the
This zero change in entropy g ! Kd!_
is due ‡!A
to the factr)su
that J
theYA Q!‡The
process A˜p!d:‡
water vapor ‡_g—_™8
was
saturated carried in the cylinder)™ …Abg–\dQ
exerts
outofreversibly,
vapor pressure
gdA p!…\2_A
a certain pressure , which isg
water at the temperature T. The system is exactly
reservoir to the cylinder. The change in the entropy of the heat reservoir is thus
i.e., no degradation occurred YA during the process.
p…g2A‡‡ \‡ …A–A…‡\)_A r2su equilibrium when the external pressure acting on the piston, Pext, equals the inter

If thezero
This evaporation
change in is carried
entropy is out
due irreversibly then
to the fact that the heat q (q<q
process was ) acting
is transferred
carried
pressure out piston, from ,the
reversibly,
on the and when the temperature of the water+wa
!d: \‡ p…A‡‡”…A —\__ )A _g—A…8 :AA…b\dA: )™ YA !bg‡pYA…\2 p…A‡‡”…A !d
—A\QY gJ YAndp\‡gdu  \‡ A–Ad pg‡‡\)_A46 Y!
2 law of thermodynamics :”…\dQ Y\‡ A˜p!d‡\gd YA p\‡gd
Introduction to the Thermodynamics of Materials
g–A…‡Ygg \‡ ”_\b!A pg‡\\gd8 YAd :…gp3.5)A_g— AN ILLUSTRATION \8 !d: !JA… ‡gbA
OF IRREVERSIBLE g‡2\__!
AND REVERSIBLE
PROCESSES
‡A_A :g—d g \‡ Kd!_ pg‡\\gdu rYAYA… Y\‡ !2”!__™
If the evaporation process is conducted irreversibly, then heat q is transferred Y!ppAd‡ from\dthe
! Q\–Ad
Consider a system of water and water vapor at the uniform temperature T contained
reservoir to the cylinder at the temperature T cylinder fitted with a frictionless piston, and let the cylinder be placed in thermal contact wi
The Second Law of Thermodynamics 49 heat reservoir which is also at the constant temperature T. This system is shown in Fig

The Second Law of Thermodynamics 49


TheHowever,
total heat appearing
the total ininthe
heat appearing cylinder
the cylinder equals
equals the heatthe heat qfrom the
q transferred
transferred from
heat reservoir plusthe heatwhich
the heat reservoir plus
is produced by the heat which
degradation of work is due to the
irreversible nature of the process. Thus degraded work, (wmax–w), equals (qrev– q), and
produced by degradation of work due to the irreversible
thus the change in the entropy of the contents of the cylinder is
nature of the process.
However, the total heat appearing in the cylinder equals the heat q transferred from the
heat reservoir plus the heat which is produced by degradation of work due to the
Thus nature
irreversible degraded
of thework, (wmax
process. –w),
Thus equals work,
degraded (qrev–(w
q), and
–w), equals (qrev– q), and
max
thuswhich,
the itchange in theq entropy
is seen, is simply /T. Thus theofchange
the incontents
the entropy of the
of the combined system
thus the change in the entropy of the contents of the cylinder is
rev
cylinder is
caused by the irreversible nature of the process is

Figure 3.2 A thermostalled piston and cylinder containing water and


water vapor.

which, it is seen, is simply qrev/T. Thus the change in the entropy The
of water
the combined system
vapor in the cylinder exerts a certain pressure , which is
saturated vapor pressure of water at the temperature T. The system is exactly
caused by the irreversible nature of the process is equilibrium when the external pressure acting on the piston, Pext, equals the inte
As qrev>q, this entropy change is positive, and thus entropy has been produced (or
pressure acting on the piston, , and when the temperature of the water+w
created) as a result of the occurrence of an irreversible process. The entropy
vapor in produced,
the cylinder equals the temperature T of the constant-temperature heat reserv
(qrev–q)/T, is termed Sirreversible ( Sirr) and is the measure of the degradation which
If the external has acting on the piston, Pext is suddenly decreased by a finite amo
pressure
irreversible nature of the process. Thus degraded work, (wmax–w), equals (qrev– q), and
thus the change in the entropy of the contents of the cylinder is
2nd law of thermodynamics
which, it is seen, is simply qrev/T. Thus the change in the entropy of the combined system
Thus the change in the entropy of the combined system caused by the irreversible
caused
nature of by the irreversible
the process is nature of the process is
which, it is seen, is simply qrev/T. Thus the change in the entropy of the combined system
caused by the irreversible nature of the process is

As qrev>q, this entropy change is positive, and thus entropy has been produced as a
As q >q, this entropy change is positive, and thus entropy has been produced (or
result of the revirreversible process
created) as a result of the occurrence of an irreversible process. The entropy produced,
(q>q,
As qrev
rev
–q)/T, is termed
this entropy changeSirreversible ( Sirrand
is positive, ) and
thus is the measure
entropy has of theproduced
been degradation
(or which has
The entropy
created) as aproduced,
occurred result (qreoccurrence
as aofresult
the v–q)/T,
of is of
termed
the process. anThus, ΔSfor
irreversible ( ΔSirrThe
theprocess.
evaporation
irreversible ) and is theproduced,
entropy
process, measure of of the
irrespective
the(qdegradation which Shas occurred
–q)/T, is termed ( Sirras a result
) and of the process
is the measure of the degradation which has
rev degree of irreversibility,
irreversible
occurred as a result of the process. Thus, for the evaporation process, irrespective of the
For the evaporation
degree process, irrespective of the degree of irreversibility,
of irreversibility,
(3.2)

(3.2)
Consideration of the condensation process shows that the work done on the system has a
2nd law of thermodynamics
If we consider the condensation process, the work done on the system has a minimum
value when the condensation is conducted reversibly, and, correspondingly, the heat
transferred from the cylinder to the heat reservoir has a minimum value qrev.

If the process is conducted irreversibly then a greater amount of work must be


performed, and the excess of this work over the minimum required is the work which is
degraded to heat in the irreversible process.
50 Introduction to the Thermodynamics of Materials

Thus,
Forfor a reversiblecondensation
a reversible condensation

and

i.e., entropy is not created.


For an irreversible condensation,
2nd law of thermodynamics
i.e., entropy is not created.
For an irreversible condensation,
For an irreversible condensation,

and

d, as q>qrev, it is seen that entropy has been created as a result of the irreversible
ocess. The entropy created is Sirr, and, thus, again, the change in the entropy of the
ter and water vapor is given by And, as q>qrev, it is seen that entropy has been created as a result of the irrevers
process. The entropy created is Sirr, and, thus, again, the change in the entropy of
water and water vapor is given by (3.3)

e important feature to be noted from Eqs. (3.2) and (3.3) is that, in going from an (3
ial state to a final state [either the evaporation or condensation of 1 mole of water at
and
e total heat appearing in the nd
2 law of thermodynamics
cylinder equals the heat q transferred from the
r plus the heat which is produced by degradation of work due to the
ature of the process. Thus degraded work, (wmax–w), equals (qrev– q), and
i.e., entropyFor
is not
the created.
condensation case
For the evaporation case
ge in the entropy of the contents of the cylinder is For an irreversible condensation,

een, is simply qrev/T. Thus the change in the entropy of the combined system
In both the cases, in going from an initial state to a final state, the left-hand sides are
e irreversible nature of being
constants, the process is respectively, to qrev/T and -qrev/T.
equal,

The difference in the entropy between the final and initial states is thus independent of
whether the process is conducted reversibly or irreversibly and, being independent of
the process path can be considered as The
being the difference between the values of a
andSecond Law of Thermodynamics 51
state function
(3.4a)
his entropy change is positive, and thus entropy has been produced (or
result of the occurrence of an irreversible process. The entropy produced,
termed Sirreversible ( Sirr) and is the measure of the degradation which has (3.4b)
result of the process. Thus, for the evaporation process, irrespective of the
Eq (3.4b) indicates that, as the change in entropy
versibility, canasbeq>q
And, determined
, it is only
seenbythat
measure-
entropy has been created
rev
2nd law of thermodynamics
ILLUSTRATION OF REVERSIBLE AND IRREVERSIBLE PROCESSES

1.  The isothermal reversible expansion of an ideal gas


2.  The free expansion of an ideal gas.

These two processes have in common that the temperature of the gas remains
constant.

Since the gas is ideal, the internal energy of the gas does not change for either
process, since the temperature does not change

In the reversible case, work is performed by the gas during its expansion, but no work
is performed by the gas during the free expansion
From the First Law,

2nd law of
∆U thermodynamics
= q−w

We haveReversible Isothermal
seen that Expansion
the internal energyofofananIdeal Gas
ideal gas depends only on its tempera-
ture. Hence, ∆ U = 0, the
Let us consider andreversible
thus, q =isothermal
w ; that is,expansion
the work done by the
of 1 mole of aexpanding
monatomicgas on
ideal
gas from the state (VA,T) to the state (VB,T), where VB > VA

VB

Sand

VA 1 mole of
1 mole of an ideal gas
an ideal gas

Heat bath at constant temperature, T Heat bath at constant temperature, T

(a) (b)
The gas passes through a continuum of equilibrium states in going from the state (VA ,T)
to the state (VB,T). Since the gas is never out of equilibrium, the process is reversible.
Figure 3.2 (a) One mole of a confined ideal gas being held at V A by a mass of sand. (b) The
mass of sand is removed
From the Firstand the∆U
Law, new= volume
q − w if the gas is VB.

* The pertinent feature of a constant-temperature heat reservoir is that it experiences only heat effects
and neither performs work nor has work performed on it. The ice calorimeter , which comprises a
piston equals the thermal energy transferred from the constant-temperature he
We calculate the work done as
rvoirtheinto theequals
piston gas. thendthermal energy transferred from the constant-temperature heat
reservoir into
We calculate 2gas. done
thethework lawasVof thermodynamics
VB
RTdV VB
∫ ∫
B
We calculate
THE SECOND LAW OF work = asPdV
theTHERMODYNAMICS
wrevdone = = RT ln 63
The internal energy of an ideal gas
VA depends
VAonlyVon its temperature.
VA Hence, ∆U = 0,
and thus, q = w VB VB
RTdV VB VB
∫∫ ∫
VB VB
RTdV
theSince
pistonVequals
B > V the
A , w
wrev =
thermal
is
w a
rev rev
energy
= PdV
positive
PdV =
transferred
=
quantity, from
in the
= =
constant-temperature
RT RT
ln
accordance ln
with the fact heatwork is
that
reservoir
done
into
by the
The work
the gas.
gas.byThe
done VA VAof thermal
thetransfer
expanding gas on VVthe VV from
energy
A piston
A
the the
equals VA toenergy
VAthermal
reservoir the gas (at con-
We calculate the work done as
transferred from the constant-temperature heat reservoir into the gas.
stant internal energy) causes a change in the entropy of the gas:
Since V B > V A , w rev is a positive quantity, in accordance with the fact that work is
>V
e V Bdone , w rev is
byAthe gas.
a positive
Thewtransfer VB
of
quantity,
thermalVB
RTdV in accordance
energy from
with
VB reservoir
the to
thegas
the
fact
(at
that
con-
work
e by stant
the gas. The transferrev =
internal energy) causes ∫of
∆Sgas
PdV =
thermal
VA a=change∫
SB − SVAin
A
qrev = wRT
energy
= the =
V entropy
T T
rev ln
from = the
ofVRthe
A
VB
reservoir to the gas (at co
ln gas:
VA
internal energy) causes a change in the entropy of the gas:
Since V B > V A , w rev is a positive quantity, in
qrevaccordance
wrev withVthe fact that work is
which
done is gas.
by the alsoThe ∆Sgasof
a positive
transfer =thermal
SB − S Aenergy
quantity. = change
The = the
from in=reservoir
the B
R lnentropy
to ofgasthe
the (at reservoir
con- is
given by q T Tw VA V
stant internal energy) causes a change in the entropy ofrev
the gas:
∆Sgas = SB − S A = rev
= = R ln B

which is also a positive quantity. The T


change T the entropy
in VAof the reservoir is
qrevq wrev VB VA
given by ∆ S = S B − S
∆gasSheat reservoir =
A= − == −∆ = R ln
S = RVln <0
TT T gas A VB
ch is also a positive quantity. The change in the entropy of the reservoir
qplus heat VAcanofbe
n bywhich
The is alsochange
total a positive
in ∆ Squantity.
the entropy
heat reservoir
The
(gas
= − change
= −∆ in reservoir)
Sgas
the
= entropy
R ln < 0 thewritten
reservoir
as is
given by T VB
∆Stotal = ∆Sgas + ∆Sreservoir = 0 (3.2)
The total change in the entropy (gas q heat reservoir)
q plus VA canVbe
A written as
2nd law of thermodynamics
Free Expansion of an Ideal Gas

consider the free expansion (i.e., expansion against zero atmospheric pressure) of 1
mole of an ideal gas from VA to VB.

Free expansion of an ideal gas is also isothermal.

The final state of the free expansion is the same as the state of the isothermal
reversible expansion process

No work is done by the gas against the piston

∆U = 0 and w = 0, which by the First Law means that q = 0


2nd law of thermodynamics
Since entropy is a state function, the change of entropy of the gas for the free
expansion must be the same as that for the isothermal expansion.

Since no thermal energy leaves the heat reservoir, ∆Sreservoir = 0

For the free expansion process, the entropy of the universe increases (∆Stotal > 0)

In the case of free expansion, there is no decrease in entropy of the heat reservoir,
since no thermal energy was absorbed by the ideal gas, since it did no work.
2nd law of thermodynamics
For the reversible isothermal expansion case, qrev = wmax.

This process yields the maximum amount of work that can be performed by the gas
during isothermal expansion

The reversible process also yields the most amount of thermal energy that can be
transferred to the gas from the heat reservoir.

The total change in entropy of the universe is zero.

For the case of the free expansion of the gas, we have seen that w = q = 0.

The work performed in these two cases of the isothermal expansion of an ideal gas
varies between 0 for free expansion (isothermal) and wmax for reversible isothermal
expansion 0 ≤ w ≤ wmax and 0 ≤ q ≤ qrev
2nd law of thermodynamics
0≤q≤q rev

The work performed in these two cases of the isothermal expansion of an ideal gas
This means that
varies between 0 for free expansion (isothermal) and wmax for reversible isothermal
expansion 0 ≤ w ≤ wmax and 0 ≤ q ≤ qrev
qrev
0 ≤ ∆Stotal ≤
0 ≤ ∆Stotal ≤ qrev/T T
∆Stotal = 0∆when
S the= 0process is reversible.
when the process is∆S ∆ Sthe process
total > 0 when
reversible. > 0 when
is irreversible.
the process is irre
total total
The maximum value of ∆ S total occurs for the completely irreversible free ex
case.
The maximum value of ∆Stotal occurs for the completely irreversible free expansion
It is important to note that the difference in entropy between the final an
states of the gas is independent of whether the process is conducted reve
Note that the difference in entropy between the final and initial states of the gas is
irreversibly.
independent of whetherInthe
going fromis state
process A to state
conducted B , or irreversibly.
reversibly

THE SECOND LAW OF THERMODYNAMICS


In going from state A to state B, q
∆S = SB − S A = + ∆Sirr
T
q
= rev
T
2nd law of thermodynamics
Reversible Isothermal Compression

Consider the reversible isothermal compression of 1 mole of an ideal gas from


the state (VB,T) to the state (VA,T)

If the gas passes through a continuum of equilibrium states in going from the state
(VB ,T) to the state (VA ,T), then

Entropy is not created during this process

Entropy is transferred from the gas to the heat reservoir, where it is measured as the
thermal energy entering divided by the temperature T

Since the compression is conducted isothermally, ΔU = 0; thus, the work done on the
gas is equal to the thermal energy withdrawn from the gas

wmax =qrev
max =
wwmax = qqrev
rev

where
where
2nd law of thermodynamics
VVAA VVAA
RTdV
RTdV V
max =
wwmax =
∫∫
VVBB
PdV ==
PdV

VVBB VV
== RT
RT ln AA
VBB

Since
Since
Since B>
VVBV >VVVA,A,w
B >A ,ww isisaanegative
negative quantity,
quantity, in
in accordance
accordance with the fact that work is
max is a negative quantity, in accordance with the fact that work is done
max
max
done
done onthe
on
on the thegas.
gas. gas.
The The
The transfer
transfer
transfer of
ofof thermal
thermal
thermal energyfrom
energy
energy fromthe
from thegas
the gas to
to the
the reservoir
reservoir causes
causes a
aachange
changeininthe
change the entropy
theentropy
entropyof ofofthe
the gas:
thegas:
gas

q w V
66 INTRODUCTION TO∆∆THE = qrev
rev w max
== max == RR ln
SSgas =THERMODYNAMICS
gas
VAA MATERIALS, SIXTH EDITION
lnOF
TT TT VVBB

which is also a negative quantity. Since there is no change in the total entropy
during the reversible compression, the change in the entropy of the reservoir is
Since
given by there is no change in the total entropy during the reversible compression, the
change in the entropy of the reservoir is given by
VB
∆Sheat reservoir = −∆Sgas = R ln >0
VA

3.8 THE ADIABATIC EXPANSION OF AN IDEAL GAS


2nd law of thermodynamics
Entropy changes for an ideal gas
2nd law of thermodynamics
ideal gas
I 5? T

2nd law of thermodynamics


V')
q - nRTln -.
AS-- ~dT.
V1
T T
84 Chemical Thermodynamics: Principles and Applications
H e n c e Isothermal Expansion of an Ideal Gas:
Calculation of ΔS for the Reversible
Calculation of AS for the Isochoric Temperature Change
dSIp
nR _
6q-Cv ~G
l ndT
AS-

I
dS-~
.
V1
CvdT
•SqrevExpansion:
Calculation of ΔS for the Reversible Adiabatic
Calculation of AS T
T for the Reversible Adiabatic Expansion

I osl ΔS_ =G0


~Sq-O
5?
dS-0
T
I d_~Ttv Cv
Calculation of ΔS for the Isobaric Temperature Change:
AS-O.
T
AS-- ~dT.
Calculation of AS
T Tfor the Isobaric Temperature Change: k
I O_~Tt
v Cv
~Sq- Cp d r T
Calculation of AS for the Isochoric Temperature
Calculation of ΔS for the Isochoric Temperature Change: Chang
•Sqrev
6q-Cv dTT Cp d T
As-JTIC~T
d S - ~ = ~ dT.
T T
CvdT
Calculation of AS for the Reversible (Equilibrium) Phase
nd of a liquid at its melting point, a (solid + solid) phase
2 law of thermodynamics
freezing
transition temperature, and the boiling of a liquid or subliming
gas at a temperature where the vapor pressure of the liquid or s
ΔS for the Reversible (Equilibrium) Phase Change:
the confining atmospheric pressure, are reversible processes
The boiling of aconstant
liquid or subliming of a solidand
temperature to a pressure.
gas at a temperature where the
The entropy change for th
vapor pressure of the liquid or solid is equal to the confining atmospheric pressure, are
easily calculated. Integrating equation (2.38) at constant T give
reversible processes that occur at constant temperature and pressure.
The First and Second Laws of The

I ~Sqrev qrev The First and Second La


AS-- ~ =
At constant pT T
AtAt constant
constant
p
qrev --P A H

so that qrev -- A H

so thatAS = ~A,H
T
where ΔH, the change in enthalpy for theAchange
H in phase
where AH,AS the
= ~change
, in enthalpy for the change in phase,
T AvapH, the enthalpy of vaporization, /Xtr~n~
enthalpy of fusion,
moles of ideal gas B at the same pressure p and temperature 7
stopcock is opened, the gas molecules mix spontaneously and irrev
2nd law of thermodynamics
an increase in entropy Ami• occurs. The entropy change can be c
recognizing that the gas molecules do not interact, since the gas
AmixS is then simply the sum of ASA, the entropy change for the e
ΔS for the Mixing of Ideal Gases gas
at Constant
A from VA T and P:+ VB) and/XSB, the entropy change for the e
to (VA
gas B from VB to (VA + V~). That is,
Consider the process where nA moles of ideal gas A are confined in a bulb of volume VA
at a pressure p and temperature T. This bulb is separated by a valve or stopcock from
m m i x S - ASA --1-A S B.
bulb B of volume VB that contains nB moles of ideal gas B at the same pressure p and
temperature T
A B A+B

When the stopcock is opened, the gas o eoL o |


molecules mix spontaneously and irreversibly .~ O | |
0 | |
I"Io
Order AS > 0 Disorder
Increase in entropy occurs.
Figure 2.13 Mixing of ideal gas A with ideal gas B at constant tem
constant total pressure. The entropy change AS is given by equation (2.

The entropy change can be calculated by recognizing that the gas molecules do not
interact, since the gases are ideal.
an increase in entropy Ami• occurs. The entropy change c
nd2 law of thermodynamics
recognizing that the gas molecules do not interact, since
AmixS is then simply the sum of ASA, the entropy change f
gas A from VA to (VA + VB) and/XSB, the entropy change f
ΔmixS is then simply the sum of ΔSA, the entropy change for the expansion of gas A
from VA to (Vgas88 B fromThermodynamics"
Chemical VB to (VA + V~).
Principles That is,
A + VB) and ΔSB, the entropy change for the expansion of gas B from VB to
and Applications
(VA+ VB).
88 Chemical Thermodynamics" Principles and Applications
m m i x Schanges
The entropy - ASA ASA--1-
andA SASBB. can be calculated from equation (2.69),
which applies
The entropy to the
changes ASAisothermal
and ASB can reversible
be calculatedexpansion
from equationof ideal
(2.69), gas, since AS is
independent
which applies to theofisothermal
the pathreversible
and theexpansion
same result
of idealisgas,
obtained
since AS for
is the expansion
The entropy independent
changes
during ΔS the and B can
spontaneous
of Athe ΔSand
path be calculated
the mixing
same process
result byasusing
is obtained for the
during expression
the the controlled
expansion for reversible
isothermal reversible
during the expansion
expansion.spontaneous
Equationof ideal
mixing gas.
process
(2.69) givesas during the controlled reversible
expansion. Equation (2.69) gives A B A+B

ASA ASA
VA + V~VA
- r/A R- In r/A R In
VA VA
+ V~
o eoL o |
.~ O | |
0 | |
I"Io
VA+ VB
A S B -- nBR In VA+ VB
A S B -- nBR In

Hence
Order AS > 0 Disorder
Hence
I VA + VB VA + VB
AmixS- R rtA In + nB In
. (2.75)
Figure 2.13 Mixing of ideal gas VA
I VA A + with
VA + VB
VB VBideal gas B at const
A m i x S - R rtA In + nB In
. (2.75)
constant total pressure. The entropyVBchange AS is given by equa
VA
Using the ideal gas equation, we can write
I RT
VA + VB VA + VB
A m i x S - R rtA In + nB In
ndThermodynamics"
. pVB (2.75)
2 law
88 Chemical
n A - -of
VA
thermodynamics
PVA
~ p(VA + VB)
VB and Applications
Principles
/7B --
Using thethe
ideal gasgas
equation,
nA + n B - -
we we RT
can can
write
RT
Using ideal equation, write
R TASB can be calculated from equation (2.69),
The entropy changes ASA and
pVB reversible expansion of ideal gas, since AS is
which applies to the isothermal
PVA p(VA + VB)
n A - - ~independent of the/7B path
-- and the samenAresult is obtained for the expansion
Combining the last + n B --
RT
during the spontaneous Tthreeprocess
Rmixing equations
as duringgives
the controlled reversible
RT
expansion.
pVB Equation (2.69) gives
/7B --
RT nA p(VA + VB)
VA
nA +=VA
n B+- Combining
-V~
ASA - r/A R In =XA the last three equations give
p(VA h+AVB)
+riB VA
V A + VB
RT
nA + n B - -
RT VA+ VB
CombiningnBR In the last
A S B -- nB nA
VBthree equations givesVA
Combining the last three equations =gives = = XB =XA
nA -]- nBnA VA -+- VB hA+riB V A + VB
Hence VA
nA VA = =XA
= =XA (2.76)
nB VB

B9
hA+riB V A + VB hA+riB V A + VB

0
0
whereAXA and I XB are
m i x S - R rtA In
VA +the
VB mole VA
+ nB In
fractions
+ VB
=. of A and =B XBin the mix
(2.75)
nB equations (2.76) andVA (2.77)VB nAinto
-]-VBnBequation-+-(2.75) and rearr
VB
= = XB nB VA (2.77)
VB
~ I~.

c~

= = XB
m

o
nA -]- nB VA -+- VB
nAequation,
Using the ideal gas -]- nB weVAcan-+-write
VB

oe
.,..

where XA and XB are the mole fractions ofwhere


A and BXA and XB Substituting
are the mole fractions
-..

in the mixture.
equations (2.76) and (2.77)
PVAinto equation (2.75) and rearranging gives the

:~
~
I

i.
2nd law of thermodynamics
2nd law of thermodynamics
The ability to calculate entropy changes by the integration of dqrev/T is strictly limited
to reversible processes.

A comparable integration using (dqirr/T) between states connected by an irreversible


process would not yield an entropy change for the process.

Entropy is a state function, the changes associated with irreversible processes can still
be calculated if a reversible path, perhaps a purely hypothetical one, can be conceived
for which dqrev/T can be evaluated.
2nd law of thermodynamics
1. Entropy is a thermodynamic state variable (function).
2. Entropy is not created when a system undergoes a reversible process; entropy is
transferred from one part of the system/surroundings to another part.
3. The total entropy of the universe increases when an irreversible process occurs.
4. For all processes, we can write ∆S′ = q/T + ∆Sirr′ and q ≤ qrev system.
5. For all processes, the entropy of the universe increases or stays the same. The
total entropy of the universe never decreases.
MM209 - Thermodynamics
Instructor : Aswani Yella
2nd law of thermodynamics
Conversion of heat into work

When two stones are rubbed together under water, the work done against the
force of friction is transformed into internal energy tending to produce a rise
of temperature of the stones.

As soon as the temperature of the stones rises


above that of the surrounding water, however, there is heating of the water.

If the mass of water is large enough, then there will be no appreciable rise of
temperature, and the water can be regarded as a heat reservoir

Since the state of the stones is the same at the end of the process as
at the beginning, the net result of the process is merely the conversion of
mechanical work into heat.
2nd law of thermodynamics
Conversion of heat into work

Similarly, when an electric current is maintained in a resistor immersed either in running


water or in a very large mass of water, there is also a conversion of electrical work into
heat, without any change in the thermodynamic coordinates of the wire.

Work of any kind W may be done on a system in contact with a reservoir, causing heat Q
to leave the system without altering the state of the system.

The system acts merely as an intermediary. It is apparent from the first law that the work
is equal to the heat, W = Q;

The transformation of work into heat is accomplished with 100 percent efficiency.
Moreover, this transformation can be continued indefinitely.
2nd law of thermodynamics
Conversion of work into heat

Isothermal expansion of an ideal gas might be a suitable process to consider in


discussing the conversion of heat into work.

In this case, there is no change of internal energy, since the temperature remains
constant, and, therefore, Q = W, or heat has been converted completely into work.

This process, however, involves a change of state of the gas. The volume increases
and the pressure decreases until atmospheric pressure is reached, at which point the
process stops. Therefore, the process of isothermal expansion cannot be used
indefinitely .
2nd law of thermodynamics
What is needed is a series of processes in which a system is brought back
to its initial state, that is, a cycle.

Each of the processes that constitute a cycle involves either the performance of work or
a flow of heat
68 between the system
INTRODUCTION and
TO THE its surroundings
THERMODYNAMICS OF MATERIALS, SIXTH EDITION

Heat reservoir at high q2 Heat q1 Heat reservoir at low


temperature t2 engine temperature t1

Work, w

For one complete cycle, let


Figure 3.3 Schematic representation of the working of a heat engine.
the symbol QH represent the heat exchanged between the high-temperature reservoir
and the system;
the symbol QL represent the heat exchanged between the low-temperature reservoir and
the system; Rumford in 1798. In the operation of a heat engine, some of the energy that has been
the symboltransferred from a the
W represent high-temperature
work exchangedheat reservoir
between is converted into work,
the system andwith
thethe
surroundings.
remainder ofQthe
All three quantities energy being transferred to a low-temperature heat reservoir. The
H, QL, and W, are expressed as absolute values, that
process is shown schematically in Figure 3.3. Treating the engine as the system, the
is, positiveFirst
numbers only.
Law gives
2nd law of thermodynamics
If QH is larger than QL and if W is done by the system, then the
machine
68 thatINTRODUCTION
causes the TO
system to undergo theOFcycle
THE THERMODYNAMICS is called
MATERIALS, aEDITION
SIXTH heat engine.

Heat reservoir at high q2 Heat q1 Heat reservoir at low


temperature t2 engine temperature t1

Work, w

Figure 3.3 Schematic representation of the working of a heat engine.


The purpose of a heat engine is to deliver work continuously to the surroundings by
performing the same cycle over and over again.
Rumford in 1798. In the operation of a heat engine, some of the energy that has been
The net work in the cycle is the output, and the heat absorbed from the high-temperature
transferred from a high-temperature heat reservoir is converted into work, with the
reservoir by the
remainder system
of the energy is thetransferred
being input. to a low-temperature heat reservoir. The
process is shown schematically in Figure 3.3. Treating the engine as the system, the
First Law gives

∆U ′ = q2 − q1 − w

Consider the steam engine, which is a typical example of a heat engine. In a steam
2nd law of thermodynamics
The thermal efficiency of the engine, symbolized by η, is defined as

where W and QH are measured in joules.

Applying the first law to one complete cycle, remembering that there is no change of
internal energy, we get

η will be unity (efficiency of 100 percent) if QL is zero.


2nd law of thermodynamics
Important characteristics of heat-engine cycles are as follows:
1. There is some process or series of processes during which there is an
absorption of heat from an external reservoir at a higher temperature.
2. There is some process or series of processes during which heat is rejected to
an external reservoir at a lower temperature.
2nd law of thermodynamics

If an engine could be built to operate in a cycle in which there is no outflow of heat


from the working substance to the low- temperature reservoir, then there would be
100 percent conversion of heat from the high-temperature reservoir into work.
2nd law of thermodynamics
No heat-engine has ever been developed that converts
the heat extracted from a reservoir at a higher
temperature into work without rejecting some heat to a
reservoir at a lower temperature.

This negative statement, which is the result


of everyday experience, constitutes the second law of
thermodynamics and has been formulated in several
ways.

The original statement of William Thomson (Kelvin) is,


"It is impossible by means of inanimate material agency
to derive mechanical effect from any portion of matter by
cooling it below the temperature of the coldest of the
surrounding objects."
2nd law of thermodynamics

In the words of Max Planck, originator of quantum


mechanics,

"It is impossible to construct an engine


which, working in a complete cycle, will produce no effect
other than the
raising of a weight and the cooling of a heat reservoir."

We can combine these statements into one equivalent


statement Kelvin-Planck statement of the second law,
thus:
It is impossible to construct an engine that, operating in a
cycle, will produce no effect other than the extraction of
heat from a reservoir and the performance of an
equivalent amount of work.
2nd law of thermodynamics

If the second law were not true, it would be possible to propel a ship across
the ocean by extracting heat from the ocean or to run a power plant by extracting heat
from the surrounding air.

Notice that neither of these "impossibilities” violates the first law of thermodynamics.

After all, both the ocean and the surrounding air contain an enormous store of internal
energy, part of which you might hope could be extracted in the form of a flow of heat.

The continuous operation of a machine that creates its own energy and thus violates
the first law is called a perpetual motion machine of the first kind.

The operation of a machine that utilizes the internal energy of only one heat reservoir,
thus violating the second law, is called a perpetual motion machine of the second kind.
2nd law of thermodynamics
HEAT ENGINE

Heat engine is a machine that takes a working substance through a cycle in such a
sequence of processes that some heat is absorbed by the system from a high-
temperature heat reservoir, a smaller amount of heat is rejected to a low-temperature
heat reservoir, and a net amount of work is done by the system on the surroundings.
2nd law of thermodynamics
REFRIGERATOR

Some heat is absorbed by the system from a heat reservoir at a low temperature, a
larger amount of heat is rejected to a heat reservoir at a high temperature, and a net
amount of work is done on the system by the surroundings.

A machine that performs a cycle in this direction is called a refrigerator, and the working
substance (system) is called a refrigerant.
2nd law of thermodynamics
QH represents the amount of heat rejected by the
refrigerant to the high-temperature reservoir;
QL represents the amount of heat absorbed by the
refrigerant from the low-temperature reservoir;
W represents the net work done on the refrigerant by the
surroundings.

Since the refrigerant undergoes a cycle, there is no change


in internal energy, and the first law becomes

That is, the heat rejected to the high-temperature reservoir


is larger than the heat extracted from the low-temperature
reservoir by the amount of work done on the refrigerant.
2nd law of thermodynamics
The purpose of a refrigerator is to extract as much heat QL
as possible from the low-temperature reservoir with the
expenditure of as little work W as possible.

Work is always necessary to transfer heat from a lower-


temperature reservoir to a higher-temperature reservoir,
because it is a fact of nature that heat does not flow
spontaneously from a lower-temperature reservoir to a
higher-temperature reservoir.

This negative statement leads us to the Clausius


statement of the second law:

It is impossible to construct a refrigerator that, operating in a cycle, will produce no


effect other than the transfer of heat from a lower-temperature reservoir to a higher-
temperature reservoir.
2nd law of thermodynamics
EQUIVALENCE OF THE KELVIN-PLANCK AND CLAUSIUS STATEMENTS

K = truth of the Kelvin-Planck statement;


-K = falsity of the Kelvin-Planck statement;

C = truth of the Clausius statement;


-C = falsity of the Clausius statement.

Two propositions or statements can be said to be equivalent when the truth of one
implies the truth of the second, and the truth of the second implies the truth of the first.

when true statements imply each other

Alternatively, equivalence can be proven when false statements imply each


other, namely,
2nd law of thermodynamics
Thus, in order to demonstrate the equivalence of K and C, falsity of one statement
implies the falsity of the second, and vice-versa

Consider a refrigerator, that requires no


work to transfer QL units of heat from a
low- temperature reservoir to a high-
X temperature reservoir

Violating the Clausius statement of 2nd law, implies -C


2nd law of thermodynamics
Suppose that a heat engine also operates between the same two reservoirs in such a
way that the same heat QL is delivered to the low-temperature reservoir

The heat engine does not violate any


law by itself

But the refrigerator and engine together


constitute a self-contained machine

This self contained machine takes heat


QH-QL from the high-temperature reservoir and
converts all this heat into work without
producing any change in the low-temperature
reservoir.
2nd law of thermodynamics

This self contained machine basically


converts all this heat into work without
producing any change in the low-
temperature reservoir.

Therefore, the refrigerator and heat engine together constitute a violation of the Kelvin-
Planck statement.
2nd law of thermodynamics

Consider a heat engine that rejects no heat


to the low-temperature reservoir

This violates the Kelvin- Planck statement

X
Suppose that a refrigerator also operates
between the same two reservoirs
2nd law of thermodynamics
Suppose that a refrigerator also operates
between the same two reservoirs and uses
up all the work performed by the engine.

Here also the refrigerator violates no law

But the engine and refrigerator together


constitute a self-contained machine

This self contained machine transfers heat QL from the low-temperature reservoir to
the high-temperature reservoir without producing any changes elsewhere.

Therefore, the engine and refrigerator together constitute a violation of the Clausius
statement.
2nd law of thermodynamics
During a part of the cycle performed by the working substance in an engine,
some heat is absorbed from a hotter reservoir;
during another part of the cycle, a smaller amount of heat is rejected to a cooler
reservoir.

Therefore, the engine is said to


operate between these two
reservoirs.

Since it is a fact of experience that


some heat is always rejected to the
cooler reservoir, the efficiency of an
actual engine is never 100 percent.
2nd law of thermodynamics
Lets say that we have at our disposal two reservoirs at given temperatures

(1) What is the maximum thermal efficiency that can be achieved by an engine
operating between these two reservoirs?

(2) What are the characteristics of such an engine?

(3) Of what effect is the nature of the working substance?

CARNOT’S THEOREM
No heat engine operating between two given reservoirs can be more efficient than a
Carnot engine operating between the same two reservoirs

CARNOT’S COROLLARY
All Carnot engines operating between the same two reservoirs have the same efficiency.

CARNOT CYCLE
A Carnot cycle is a set of processes that can be performed by any thermodynamic
system whatsoever, whether hydrostatic, chemical, electrical, magnetic, or otherwise.
2nd law of thermodynamics
The system or working substance is imagined first to be in thermal equilibrium with a
reservoir at the low temperature TL .

Four processes are then performed in the following order:

1.  A reversible adiabatic process is performed in such a direction that the temperature
rises to that of the high-temperature reservoir, TH.

2. The working substance is maintained in contact with the reservoir at TH, and a
reversible isothermal process is performed in such a direction and to such an extent
that heat QH is absorbed from the reservoir.

3. A reversible adiabatic process is performed in a direction opposite to process 1 until


the temperature drops to that of the low-temperature reservoir, TL .

4. The working substance is maintained in contact with the reservoir at T L , and a


reversible isothermal process is performed in a direction opposite to process 2 until the
working substance and the surroundings are in their initial states. During this process,
heat QL is rejected to the low-temperature reservoir.
2nd law of thermodynamics
An engine operating in a Carnot cycle is called a Carnot engine.

A Carnot engine operates between two reservoirs in a particularly simple way. All the
absorbed heat enters the system at a constant high temperature, namely, that
of the hotter reservoir.

Also, all the rejected heat leaves the system at a constant low temperature, that of the
cooler reservoir.

Notice that the exchange of heat in the Carnot cycle is unlike the situation for idealized
real engines, which need a series of reservoirs to exchange heat during the constant-
volume or constant-pressure processes in order to achieve reversibility.

In the Carnot cycle, a single reservoir exchanges heat during a constant-temperature


process.

Since all four processes are reversible, the Carnot engine is a reversible engine.
2nd law of thermodynamics
EXAMPLES OF CARNOT CYCLES

The simplest example of a Carnot cycle is that of a gas which can be depicted on a PV
diagram.

The gas is initially in the state represented by


the point 1.

The four processes will then be:


1.  Process 1 to 2, reversible adiabatic compression until
the temperature rises to TH·

2. Process 2 to 3, reversible isothermal expansion until


any desired point, such as 3, is reached.

3. Process 3 to 4, reversible adiabatic expansion until the


temperature drops to TL.

4. Process 4 to 1, reversible isothermal compression until


the original state is reached.
2nd law of thermodynamics
For a two-phase system, such as steam and
water, the Carnot cycle has a shape quite
different from a gaseous system.

The dashed line LA VA denotes the isothermal and


isobaric vaporization of the liquid at the higher
temperature TH;

The dashed line L B VB denotes the isothermal and


isobaric condensation of the vapor at the lower
temperature T L .

Any point between the dashed lines L and V represents a mixture of liquid and vapor.
2nd law of thermodynamics
Starting at the point 1, the four processes in the
Carnot cycle are as follows:

1.  Process 1 to 2, reversible adiabatic compression until the


temperature rises to T H .
2. Process 2 to 3, reversible isothermal isobaric vaporization
until any arbitrary point, such as 3, is reached.
3. Process 3 to 4, reversible adiabatic expansion until the
temperature drops to T L.
4. Process 4 to 1, reversible isothermal isobaric
condensation until the initial state is reached.

During the isothermal vaporization 2 to 3, heat QH is absorbed from the hotter reservoir
at TH .

During the isothermal condensation 4 to 1, heat QL is rejected to the cooler reservoir at


TL .
2nd law of thermodynamics

A Carnot cycle using an Carnot cycle of a paramagnetic substance


electrochemical cell (acid battery) on which obeys Curie's law is shown on a H-M
an E-z diagram diagram. Lines 0TH and 0TL represent
The lines marked TH and TL represent isothermal lines at the temperatures
isothermal and constant emf curves at TH and TL , respectively
the two temperatures of the reservoirs.
The point 1 indicates that the cell is
well charged.
2nd law of thermodynamics
The net work done in one cycle by any Carnot engine
can be adjusted to any arbitrary amount by choosing
the position of the point 3

By adjusting the extent of the isothermal process 2 to


3, we can control the amount of heat QH from the high-
temperature reservoir.

The nature of the working substance determines the thermodynamic coordinates used
to plot a Carnot cycle, as well as the shape of the cycle.

If an engine is to operate between only two reservoirs and still operate in a reversible
cycle, then it must be a Carnot engine.
2nd law of thermodynamics
CARNOT REFRIGERATOR

Since a Carnot cycle consists of


reversible processes, it may be
performed in either direction.

When it is performed in a direction


opposite, it is a refrigeration cycle

The important feature of a Carnot refrigeration cycle, which distinguishes it from any
general reversed engine cycle, is that the quantities QH, QL, and W are numerically
equal to those quantities when the cycle is performed in the opposite direction.

Example, exactly same amount of heat that is absorbed by the Carnot engine from the
high-temperature reservoir is rejected to the high-temperature reservoir when the cycle
is reversed.
2nd law of thermodynamics
CARNOT'S THEOREM AND COROLLARY
No heat engine operating between two given reservoirs can be more efficient than a
Carnot engine operating between the same two reservoirs.

Imagine a Carnot engine R, which is reversible, and any other engine I, which is
irreversible, working between the same two reservoirs and adjusted so that they both
deliver the same amount of work W.

Carnot engine R Irreversible engine I

1. Absorbs heat QH from the high- 1.  Absorbs heat QH’ from the high-
temperature reservoir. temperature reservoir.

2. Performs work W. 2. Performs work W.

3. Rejects heat QH-W to the low- 3. Rejects heat QH’-W to the low-
temperature reservoir. temperature reservoir.

4. Efficiency 4. Efficiency
2nd law of thermodynamics
Let us assume that the efficiency of the engine I is greater than that of R.

Now let the engine I drive the Carnot engine R backward as a Carnot refrigerator.
2nd law of thermodynamics
The engine and the refrigerator coupled together in this
way constitute a self-contained machine, since all the
work needed to operate the refrigerator is supplied by the
engine.

The net heat extracted from the low-temperature reservoir


is

which is positive.

The net heat delivered to the high-temperature reservoir


is

Therefore, the effect of this self-contained machine is to transfer units of


heat from a low-temperature reservoir to a high-temperature reservoir without work being
done by the surroundings.

Violation of Clausius Statement


2nd law of thermodynamics
All Carnot engines operating between the same two reservoirs have the same efficiency.

Consider two Carnot engines R1 and R2, operating between the same two reservoirs.

If we imagine R1driving R2 backward, then Carnot's theorem states that

If R2 drives R1 backward, then

But, the efficiency of the first reversible engine cannot be both less than or equal to the
efficiency of the second reversible engine, as well as greater than or equal to the
efficiency of the second reversible engine.

Therefore, the efficiencies of the two reversible engines can only be equal

Important conclusion: The nature of the working substance which is undergoing the
Carnot cycle has no influence on the efficiency of the Carnot engine.
2nd law of thermodynamics

1.  The maximum thermal efficiency that can be achieved by a heat engine operating
between two heat reservoirs at different temperatures is the efficiency of a Carnot
engine operating between the same two reservoirs.

2. The essential characteristic of a Carnot engine is that it is reversible and


operates between two reservoirs, rather than two series of reservoirs.

3. The superior efficiency of the Carnot cycle is due to its absorbing all heat at the
highest temperature and rejecting all heat at the lowest temperature.

4. Furthermore, a Carnot engine is independent of the working substance of


the system.
2nd law of thermodynamics
Efficiency of a Carnot cycle is independent of working substance and depends only on
the temperature.

The Carnot engine provides the basis for the thermodynamic temperature scale.

A Carnot engine is independent of the working substance of the system

The thermal efficiency is given by

The efficiency depends only on the two temperatures of the reservoirs,

Where φ(TH, TL) is an unknown function of the two temperatures.

Rearranging the above two equations, we get

where f (TH, TL) is also an unknown function of the two temperatures.


2nd law of thermodynamics
Lets take three Carnot engines operating between three reservoirs with T1 > T3 > T2
2nd law of thermodynamics
For engine RA,

Consider the second Carnot engine RB and


third Carnot engine RC.

Since the heat Q3 rejected by the second


Carnot engine RB is absorbed by the third
Carnot engine RC, both engines working
together are equivalent to the first
Carnot engine RA.

Thus, engine RB absorbs the same heat Q1 from the reservoir at T1 that engine RA
absorbs.
So, for engine RB ,
2nd law of thermodynamics
Engine RA rejects heat Q2 to the low-
temperature reservoir, so engine Rc
must also reject heat Q2 to the low-
temperature reservoir. Thus, for engine
Rc,
2nd law of thermodynamics

The ratio on the right is defined as the ratio


of two thermodynamic temperatures and is
denoted by T1/T2.

Thus, two temperatures on the thermodynamic scale are to each other as the
absolute values of the heats absorbed and rejected, respectively, by a Carnot
engine operating between reservoirs at these temperatures

The thermodynamic temperature scale is independent of the specific characteristics


of any particular substance
2nd law of thermodynamics

So, the Carnot engine supplies the universality that is lacking in the ideal-gas
temperature scale.

Finally, the thermodynamic temperatures are called "absolute" temperatures, because


they are independent of any material.

Kelvin was forced to choose a linear function of temperature, because all the scientific
and engineering data had been obtained from the mercury-in-glass thermometer, which
is essentially linear over its useful range.

As a result, on the thermodynamic scales now in use (Kelvin or Rankine), the


temperatures vary from 0 to +infinity for ordinary systems.

The advantage of the logarithmic scale is that absolute zero is far removed from the
normal freezing point of water, whereas, on the linear scale, absolute zero is "only" a few
hundred degrees below the ice point.
2nd law of thermodynamics
At first thought, it might seem that the ratio of two Kelvin temperatures
would be impossible to measure, since a Carnot engine is an ideal engine, quite
impossible to construct.

The ratio of two Kelvin temperatures is the ratio of two heats that are transferred
during two isothermal processes bounded by the same two adiabatic curves.

The two adiabatic boundaries may be located experimentally, and the heats
transferred during two isothermal "nearly reversible" processes can be measured with
considerable precision.

As a matter of fact, this is one of the methods used in measuring temperatures below 1K.
2nd law of thermodynamics
To complete the definition of the thermodynamic scale, we assign the arbitrary value of
273.16 K to the temperature of the triple point of water TTP.

For a Carnot engine operating between reservoirs at the temperatures T and TTP, we
have

In the thermodynamic temperature scale, Q plays the role of a "thermometric property"


for a Carnot cycle, just as pressure is the thermometric property for a constant-volume
gas thermometer.
2nd law of thermodynamics
ABSOLUTE ZERO AND CARNOT EFFICIENCY

The smaller the value of Q , the lower the corresponding T. The smallest possible
value of Q is zero, and the corresponding T is absolute zero.

Thus, if a system undergoes a reversible isothermal process without transfer of heat,


the temperature at which this process takes place is called absolute zero.

In other words, at absolute zero, an isotherm and an adiabatic are identical.

The definition of absolute zero holds for all substances and is, therefore, independent
of the specific properties of any arbitrarily chosen substance.
2nd law of thermodynamics
A Carnot engine absorbing heat QH from a hotter reservoir at TH and rejecting heat QL to
a cooler reservoir at TL has an efficiency

For a Carnot engine to have an efficiency of 100 percent, it is clear that TL must be zero.

Only when the lower temperature reservoir is at absolute zero, all the heat will be
converted into work.
2nd law of thermodynamics
EQUALITY OF IDEAL-GAS AND THERMODYNAMIC TEMPERATURES

The ideal-gas temperature was defined in terms of the ratio of the pressure P to the
pressure of the system at the triple point of water PTP in the limit as PTP approaches
zero.

A Carnot cycle of an ideal gas can be depicted on a PV


diagram

The two isothermal processes 2 to 3 at temperature θ1


and 4 to 1 at temperature θ2 are represented by
equilateral hyperbolas
2nd law of thermodynamics
For any infinitesimal reversible process of an ideal gas, the first law may be written as

Applying this equation to the isothermal process 2 to 3, the heat absorbed is

Similarly, for the isothermal process 4 to 1, the heat


rejected is
2nd law of thermodynamics
Since the process 1 to 2 is adiabatic, we may write, for any infinitesimal change

Similarly, for the adiabatic process 3 to 4,


2nd law of thermodynamics

If θ1 and T1 refer to any temperature, and θ2 and T2 refer to the triple point of
water, then

The thermodynamic temperature is,


therefore, numerically equal to the ideal-
gas temperature and, in the proper range,
Since θTP= TTP = 273.16 K, it follows that may be measured with a gas thermometer.
MM209 - Thermodynamics
Instructor : Aswani Yella
2nd law of thermodynamics

In the words of Max Planck, originator of quantum


mechanics,

"It is impossible to construct an engine


which, working in a complete cycle, will produce no effect
other than the
raising of a weight and the cooling of a heat reservoir."

We can combine these statements into one equivalent


statement Kelvin-Planck statement of the second law,
thus:
It is impossible to construct an engine that, operating in a
cycle, will produce no effect other than the extraction of
heat from a reservoir and the performance of an
equivalent amount of work.
2nd law of thermodynamics
The purpose of a refrigerator is to extract as much heat QL
as possible from the low-temperature reservoir with the
expenditure of as little work W as possible.

Work is always necessary to transfer heat from a lower-


temperature reservoir to a higher-temperature reservoir,
because it is a fact of nature that heat does not flow
spontaneously from a lower-temperature reservoir to a
higher-temperature reservoir.

This negative statement leads us to the Clausius


statement of the second law:

It is impossible to construct a refrigerator that, operating in a cycle, will produce no


effect other than the transfer of heat from a lower-temperature reservoir to a higher-
temperature reservoir.
2nd law of thermodynamics
Lets say that we have at our disposal two reservoirs at given temperatures

(1) What is the maximum thermal efficiency that can be achieved by an engine
operating between these two reservoirs?

(2) What are the characteristics of such an engine?

(3) Of what effect is the nature of the working substance?

CARNOT’S THEOREM
No heat engine operating between two given reservoirs can be more efficient than a
Carnot engine operating between the same two reservoirs

CARNOT’S COROLLARY
All Carnot engines operating between the same two reservoirs have the same efficiency.

CARNOT CYCLE
A Carnot cycle is a set of processes that can be performed by any thermodynamic
system whatsoever, whether hydrostatic, chemical, electrical, magnetic, or otherwise.
2nd law of thermodynamics

1.  The maximum thermal efficiency that can be achieved by a heat engine operating
between two heat reservoirs at different temperatures is the efficiency of a Carnot
engine operating between the same two reservoirs.

2. The essential characteristic of a Carnot engine is that it is reversible and


operates between two reservoirs, rather than two series of reservoirs.

3. The superior efficiency of the Carnot cycle is due to its absorbing all heat at the
highest temperature and rejecting all heat at the lowest temperature.

4. Furthermore, a Carnot engine is independent of the working substance of


the system.
2nd law of thermodynamics
An isothermal process or an adiabatic process is represented by a different curve on
each diagram.

But it is desired to formulate general principles that apply to all systems.

If we let the symbol Y denote any generalized force and the symbol X its corresponding
generalized displacement, a generalized work diagram in which Y is plotted against X
may be used to depict processes common to all systems

Work diagrams in which a generalized force such as P, is plotted against the


corresponding generalized displacement V, L, A, Z, or have been used to indicate
processes of various systems.
2nd law of thermodynamics
Consider a reversible process represented by the smooth curve i to f on the
generalized work diagram.

The dashed curves through i and f, respectively,


represent portions of adiabatic processes.

Let us draw a curve a to b, representing an


isothermal process, in such a way that the area
under the smooth curve i is equal to the area under
the zigzag sequence of processes, path iabf

Then, the work done in traversing both paths is the same


2nd law of thermodynamics
From the 1st law

But, since no heat is transferred in the two adiabatic


processes ia and bf, we have

If we are given, therefore, a reversible process in which the temperature may


change in any manner, it is always possible to find a reversible zigzag path
between the same two states, consisting of an adiabatic process followed by an
isothermal process followed by an adiabatic process, such that the heat transferred
during the isothermal segment is the same as that transferred during the
original process.
2nd law of thermodynamics
Now, consider the smooth closed curve on the generalized work diagram.

Since no two adiabatic lines can intersect,


a number of adiabatic lines may be drawn,
dividing the cycle into a number of
adjacent strips.

A zigzag closed path may now be drawn, consisting of alternate adiabatic and
isothermal portions, such that the heat transferred during all the isothermal portions is
equal to the heat transferred in the original cycle.
2nd law of thermodynamics
Consider the two isothermal processes ab and cd at the temperature T1 and T2
respectively.

During the process ab conducted at


temperature T1, heat Q1 is absorbed,
and the process cd conducted at the
temperature T2, heat Q2 is
rejected.

Since ab and cd are bounded by the


same adiabatic curves, abed is a
Carnot cycle, and we so we can write
2nd law of thermodynamics
For the sake of simplicity, we have been considering only the absolute values of heat
entering or leaving a system, thus ignoring the sign convention

Let us now return to the sign convention


and regard any Q as an algebraic symbol,
positive for heat absorbed by a system
and negative for heat rejected from a system.
We may then write

where Q1 is a positive number and


Q2 is a negative number.
2nd law of thermodynamics
Since the isothermal curves ef and gh are bounded by the same two adiabatic
curves, efgh is also a Carnot cycle

If a similar equation is written for each pair of


isothermal curves bounded by the same two
adiabatic curves and if all the equations are
added, then the result obtained is that

Since no heat is transferred during the adiabatic portions of the zigzag cycle,
we may write

where the summation is taken over the entire zigzag cycle consisting of Carnot
cycles, j in number.
2nd law of thermodynamics
Now, imagine the cycle divided into a very large number of strips by
drawing a large number of adiabatic curves close together.

If we connect these adiabatic curves


with small isothermal curves, then a
zigzag path may be traced that can
be made to approximate the original cycle
as closely as we want.

When these isothermal processes


become infinitesimal, the ratio dQ/T for an infinitesimal isothermal between
two adjacent adiabatic curves is equal to the ratio dQ/T for the infinitesimal
piece of the original cycle bounded by the same two adiabatic curves.
2nd law of thermodynamics
In the limit, therefore, for any reversible cycle, we can write

The circle through the integral sign


signifies that the integration takes place
over the complete cycle, and the letter
R emphasizes the fact that the equation
is true only for a reversible cycle.

This result, known as Clausius' theorem, is one part of Clausius' mathematical


statement of the second law.
2nd law of thermodynamics
For every infinitesimal amount of heat that enters a system during an infinitesimal
portion of a reversible process, there is an equation

It follows, therefore, that the total amount of heat transferred in a reversible


process is given by

This integral can be interpreted graphically as the area under a curve on a


diagram in which T is plotted along the y-axis and S along the x-axis, a so-
called "TS diagram.”

The shape of the curve on the TS diagram is determined by the kind of reversible
process that the system undergoes.
2nd law of thermodynamics
An isothermal process is a horizontal line
In the case of a reversible adiabatic process

Also, for an adiabatic process,

So, if T is not zero, then

and S is constant.

Therefore, during a reversible adiabatic process, the entropy


of a system remains constant, or, in other words, the system undergoes an
isentropic process.

An isentropic process on a TS diagram is obviously a vertical line, called an "isentrope.”


2nd law of thermodynamics
Other processes can also be plotted on a TS diagram. For a reversible isobaric
process, the curve has a slope,

Similarly, by imposing the condition of constant


Volume, the slope of a reversible isochoric
process is given by

The slopes are independent of the nature of the hydrostatic system, because the
requirement of constant pressure and constant volume eliminated the equation of
state of the ideal gas
2nd law of thermodynamics
Two isothermal and the two adiabatic
processes that make up any Carnot cycle form
a rectangle on a TS diagram, regardless of the

Temperature
nature of the working substance

Only reversible processes may be plotted on a


TS diagram, because of the definition of
entropy

Entropy

The TS diagram is particularly convenient for


representing all the idealized reversible cycles
for various heat engines.
2nd law of thermodynamics
The TS diagram is particularly convenient for
representing all the idealized reversible cycles
for various heat engines.

The closed curve consisting of an upper portion


R1 and a lower portion R2 represents any
reversible engine cycle that is not a
Carnot cycle.

The area under R1 (positive area) is equal to the positive heat Q1 absorbed by
the system, and the area under R2 (negative area) is equal to the negative heat
Q2 rejected by the system.

The area inside the closed curve is, therefore, Q1-Q2, or W.

The thermal efficiency of the engine is W/Q1, which may be measured directly from
the diagram.
2nd law of thermodynamics
The first part of the second law considered only reversible processes. The
second part deals with irreversible processes. For a reversible cycle

Let us consider an irreversible cycle and


calculate its closed integral.

High-temperature reservoir at T1 supplying a small quantity of heat


dQ1 to an auxiliary reversible engine R.

The purpose of R is to provide


reversible heat for the irreversible engine I.

Engine R rejects a small amount


of heat dQ at temperature T that is supplied
to the irreversible engine I.
2nd law of thermodynamics
Engine R rejects a small amount of heat dQ at temperature T that is supplied to
the irreversible engine I.

Engine I does a small amount of work dW


during an irreversible cycle, so the combined system
of engine R and engine I also performs an
irreversible cycle.

The net work of the combined system, according to


the first law, equals dQ1.

But the net work cannot be positive, according to the Kelvin-Planck


statement of the second law, since the combined system
exchanges heat with a single reservoir.

So, dQ1 cannot be positive.

Moreover, if dQ1 equals zero, then, at the end of the cycle, engine I and its
surroundings have returned to their original state. This result, however, is
contrary to the irreversibility of engine I. So, we conclude,
2nd law of thermodynamics
But the net work cannot be positive, according to the Kelvin-Planck
statement of the second law, since the combined system
exchanges heat with a single reservoir.

So, dQ1 cannot be positive.

Moreover, if dQ1 equals zero, then, at the end of the cycle,


engine I and its surroundings have returned to their original state.
This result, however, is contrary to the irreversibility of engine I.
So, we conclude,

Engine I generates heat that flows out of the system.

From the definition of the thermodynamic temperature scale,


in differential form for reversible engine R,
2nd law of thermodynamics
Integrating around a cycle,

However, T1 is the constant temperature of the reservoir, so

The heat dQ rejected from R is absorbed by I, so, dQR=dQI.

Substituting this expression and recognizing that the closed integral on the
left now applies to the irreversible system, we obtain
2nd law of thermodynamics
Since T1> 0, the result is

This equation provides the second part of the second law and is known as
the inequality of Clausius.

It states that for an internally irreversible cycle, the closed integral I dQ/T of the ratio of
the heat absorbed by a system to the temperature at which the heat is received is
always less than zero.

The closed integral is less than zero for an irreversible cycle and equal to zero for a
reversible cycle.

Combining the two equations yields Clausius' mathematical statement of the second
law:
2nd law of thermodynamics
HEAT AND ENTROPY IN IRREVERSIBLE PROCESSES

Consider a cycle in which a system begins


in an initial equilibrium state i, passes
during an irreversible process I to a final
equilibrium state f, and then returns by a
reversible process R to the initial state i,

Since entropy is a state function, its closed


integral is always zero:
2nd law of thermodynamics
Since entropy is a state function, its closed integral is always zero:

From the definition of entropy,


2nd law of thermodynamics
The term reversible adiabatic implies the term isentropic.

Isentropic, does not necessarily imply reversible adiabatic.

For an isentropic process, in general, we have

It follows that for an isentropic process, either


dQ = 0 reversible,
Or dQ < 0 irreversible.

Thus, reversible isentropic implies adiabatic, and isentropic adiabatic implies


reversible. But, irreversible isentropic is not adiabatic dQ < 0 and implies that
heat flows out of the system.
2nd law of thermodynamics
ENTROPY AND THE CRITERION FOR EQUILIBRIUM

Spontaneous process is, irreversible, and the movement of the system from its initial
non-equilibrium state to its final equilibrium state is accompanied by an increase in the
entropy of the system.

The attainment of the equilibrium state coincides with the entropy reaching a maximum
value, and hence, for such systems, entropy can be used as a criterion for determining
the equilibrium state.

In an isolated system of constant internal energy, U, and constant volume, V,


equilibrium is attained when the entropy of the system is at maximum, consistent with
the fixed values of U and V.
2nd law of thermodynamics
ENTROPY AND THE CRITERION FOR EQUILIBRIUM
Consider the chemical reaction occurring in anLAW
THE SECOND adiabatic enclosure at constant volume
OF THERMODYNAMICS

A+B=C+D

Starting with A and B, the reaction will


proceed from left to right as long as the

Entropy
entropy of the system is thereby increased; Equilibrium
or, conversely, starting with C and D, the
reaction will proceed from right to left,
again provided that the entropy of the
system is thereby increased. (A + B) Composition (C + D)

Figure 3.7 Schematic representation of the entropy of a closed system conta


A point is reached along the reaction coordinate
+ D as at which ofthe
a function theentropy of reaction
extent of the the system
A + B has
= C + D at co
its maximum value. energy and volume.

further reaction in either direction would decrease the entropy and, h


occur spontaneously. This concept will be utilized when we discuss th
gases in Chapter 11.
2nd law of thermodynamics
Suppose one wants to cool an object with a refrigerator
to a desired low temperature, that is, to lower the
temperature of a body of finite mass from the
temperature T1 of its surroundings to any desired low
temperature T2.

A refrigerator operating in a cycle between a reservoir


at T1 and the body itself is utilized, and, after several
complete cycles have been completed, a
quantity of heat Q has been removed from the body, a
quantity of work W has been supplied to the
refrigerator, and a quantity of heat Q + W has been
rejected to the reservoir
2nd law of thermodynamics
Applying the entropy principle, we obtain

Multiplying by T1 and transposing, we get

Smallest possible value for W is

The calculated value of W(min) is used to provide an estimate of the minimum cost of
operation of the refrigerator.
2nd law of thermodynamics
Dependence of entropy on temperature

Dependence of entropy on temperature can be calculated at constant volume as


follows:

δ q rev dU PdV C V
dS = = + = dT = C V d ln T
T T T T
T2
ΔSV = S2 − S1 = ∫ C V d ln T
T1

Dependence of entropy on temperature can be calculated at constant pressure as


follow:

δ q rev 1 1 1 C dT
dS = = [dU + d (PV )] = d (U + PV ) = dH = P = C P d ln T
T T T T T
T2
ΔSP = S2 − S1 = ∫ C p d ln T
T1
2nd law of thermodynamics
Volume Dependence of entropy
We know; δ q rev 1
dS = = [dU + d (PV )]
T T

and ⎛∂U⎞ ⎛∂U⎞


dU = ⎜⎜ ⎟⎟ dT + ⎜⎜ ⎟⎟ dV
⎝ ∂ T ⎠V ⎝ ∂ V ⎠T

1 ⎛∂U⎞ 1 ⎡⎛ ∂ U ⎞ ⎤
dS = ⎜⎜ ⎟⎟ dT + ⎢⎜⎜ ⎟⎟ + P ⎥ dV
So T ⎝ ∂ T ⎠V T ⎢⎣⎝ ∂ V ⎠T ⎥⎦

As S is function of state therefore the above expression forms an exact differentials.


Hence
∂ ⎡1 ⎛∂U⎞ ⎤ ∂ ⎡1 ⎛∂U⎞ P ⎤
⎢ ⎜⎜ ⎟⎟ ⎥ = ⎢ ⎜⎜ ⎟⎟ + ⎥
∂ V ⎢⎣ T ⎝ ∂ T ⎠ V ⎥⎦ ∂ T ⎢⎣ T ⎝ ∂ V ⎠T T ⎥⎦ V
T
2nd law of thermodynamics
Volume Dependence of entropy

On simplification the above expression yields:


⎛∂P⎞ ⎛∂U⎞
T ⎜⎜ ⎟⎟ = ⎜⎜ ⎟⎟ + P
⎝ ∂ T ⎠ V ⎝ ∂ V ⎠T

So we can write
1 ⎛∂U⎞ ⎛ ∂P⎞
dS = ⎜⎜ ⎟⎟ dT + ⎜⎜ ⎟⎟ dV
T ⎝ ∂ T ⎠V ⎝ ∂ T ⎠V
And under isothermal condition dT = 0 lead to the following expression:

⎛ ∂P ⎞
dS T = ⎜⎜ ⎟⎟ dV
⎝ ∂ T ⎠V
2nd law of thermodynamics
Volume Dependence of entropy
⎛ ∂P ⎞
dS T = ⎜⎜ ⎟⎟ dV
⎝ ∂ T ⎠V
⎛∂P⎞
In case of gas one can directly integrate the above expression to calculate the ⎜⎜
∂ T
⎟⎟
⎝ ⎠V
change in entropy during a process.
However, in case of solid and liquids, the equation of state is not known and
can also not be determined experimentally. Hence in such cases this partial
differential is required to be expressed in terms of some experimentally
determinable parameters. For this purpose the reciprocity theorem is used to write
the following:
⎛ ∂P⎞ ⎛∂V⎞ ⎛ ∂P ⎞
⎜⎜ ⎟⎟ = − ⎜⎜ ⎟⎟ .⎜⎜ ⎟⎟
⎝ ∂ T ⎠V ⎝ ∂ T ⎠P ⎝ ∂ V ⎠T
2nd law of thermodynamics
Volume Dependence of entropy
•  Isobaric coefficient of volumetric thermal expansion of a material (α) is
given as
1 ⎛∂V⎞
α = ⎜⎜ ⎟⎟
V ⎝ ∂ T ⎠P
•  Isothermal compressibility of a material (β) is given as
1 ⎛∂V⎞
β = − ⎜⎜ ⎟⎟
V ⎝ ∂ P ⎠T
•  So
α
dS = dV
β
Which on integration will yield the change in entropy for a change in volume
from V1 to V2 under isothermal condition
2nd law of thermodynamics
Pressure dependency of entropy
We know: δ q rev 1 P 1
dS = = dU + dV = (dU + P dV )
T T T T
From the definition of the enthalpy, one can get the total differential dH which can
be expressed as

dH = dU + P dV + VdP
1 V
dS = dH − dP
T T

⎛∂H⎞ ⎛∂H⎞
dH = ⎜⎜ ⎟⎟ dT + ⎜⎜ ⎟⎟ dP
⎝ ∂ T ⎠P ⎝ ∂ P ⎠T
2nd law of thermodynamics
Pressure dependency of entropy
After substitution, we get

1 ⎛∂H⎞ ⎡ 1 ⎛ ∂ H ⎞ V⎤
dS = ⎜⎜ ⎟⎟ dT + ⎢ ⎜⎜ ⎟⎟ − ⎥ dP
T ⎝ ∂ T ⎠P ⎢⎣ T ⎝ ∂ P ⎠ T T ⎥⎦
The equation is an exact differential because entropy being function of state.
Therefore,

∂ ⎡1 ⎛∂H⎞ ⎤ ∂ ⎡1 ⎛ ∂ H ⎞ V⎤
⎢ ⎜⎜ ⎟⎟ ⎥ = ⎢ ⎜⎜ ⎟⎟ − ⎥
∂ P ⎢⎣ T ⎝ ∂ T ⎠ P ⎥⎦ T ∂ T ⎢⎣ T ⎝ ∂ P ⎠ T T ⎥⎦ P

On simplification this yields

1 ⎡⎛∂H⎞ ⎤ ⎛∂V⎞
⎢ ⎜⎜ ⎟⎟ − V ⎥ = ⎜⎜ ⎟⎟
T ⎢⎣ ⎝ ∂ P ⎠T ⎥⎦ P ⎝ ∂ T ⎠ P
2nd law of thermodynamics
Pressure dependency of entropy
•  So after substitution we can write
1 ⎛∂H⎞ ⎛∂V⎞
dS = ⎜⎜ ⎟⎟ dT + ⎜⎜ ⎟⎟ dP
T ⎝ ∂ T ⎠P ⎝ ∂ T ⎠P

•  For an isothermal process the above expression yields,

⎛ ∂V ⎞
dST = − ⎜⎜ ⎟⎟ P dP = − α V dP
⎝ ∂T ⎠

•  On integration, one can calculate the change in entropy for a change in pressure from P1 to P2
under isothermal conditions.
2nd law of thermodynamics
Relationship between CP & CV
•  We have derived the following relationships:

⎛∂U⎞ ⎛ ∂P⎞ ⎛∂H⎞ ⎛∂V⎞


⎜⎜ ⎟⎟ = T ⎜⎜ ⎟⎟ − P ⎜⎜ ⎟⎟ = V − T ⎜⎜ ⎟⎟
⎝ ∂ P ⎠T ⎝ ∂ T ⎠P
⎝ ∂ V ⎠T ⎝ ∂ T ⎠V

⎛ ∂P⎞ ⎛∂V⎞ ⎛ ∂P ⎞
⎜⎜ ⎟⎟ = − ⎜⎜ ⎟⎟ .⎜⎜ ⎟⎟
⎝ ∂ T ⎠V ⎝ ∂ T ⎠P ⎝ ∂ V ⎠T

1 ⎛∂V⎞ 1 ⎛∂V⎞
α = ⎜⎜ ⎟⎟ β = − ⎜⎜ ⎟⎟
V ⎝ ∂ T ⎠P V ⎝ ∂ P ⎠T
2nd law of thermodynamics
•  We know the following expression
⎛ ∂U ⎞ ⎛ ∂V ⎞ ⎛ ∂V ⎞ ⎛ ∂ V ⎞ ⎡⎛ ∂ U ⎞ ⎤
C P − CV = ⎜⎜ ⎟⎟ ⎜⎜ ⎟⎟ + P ⎜⎜ ⎟⎟ = ⎜⎜ ⎟⎟ ⎢⎜⎜ ⎟⎟ + P⎥
⎝ ∂ V ⎠T ⎝ ∂T ⎠P ⎝ ∂ T ⎠ P ⎝ ∂ T ⎠ P ⎢⎣⎝ ∂ V ⎠T ⎥⎦

⎛∂U⎞
•  Elimination of from the above equation
⎜⎜ ⎟⎟
⎝ ∂ V ⎠T
leads to the relation
⎛ ∂P⎞ ⎛ ∂V ⎞
C P − C V = T ⎜⎜ ⎟⎟ ⎜⎜ ⎟⎟
⎝ ∂ T ⎠V ⎝ ∂ T ⎠P

α2 V T
•  Or CP − CV =
β
MM209 - Thermodynamics
Instructor : Aswani Yella
2nd law of thermodynamics

In the words of Max Planck, originator of quantum


mechanics,

"It is impossible to construct an engine


which, working in a complete cycle, will produce no effect
other than the
raising of a weight and the cooling of a heat reservoir."

We can combine these statements into one equivalent


statement Kelvin-Planck statement of the second law,
thus:
It is impossible to construct an engine that, operating in a
cycle, will produce no effect other than the extraction of
heat from a reservoir and the performance of an
equivalent amount of work.
2nd law of thermodynamics
The purpose of a refrigerator is to extract as much heat QL
as possible from the low-temperature reservoir with the
expenditure of as little work W as possible.

Work is always necessary to transfer heat from a lower-


temperature reservoir to a higher-temperature reservoir,
because it is a fact of nature that heat does not flow
spontaneously from a lower-temperature reservoir to a
higher-temperature reservoir.

This negative statement leads us to the Clausius


statement of the second law:

It is impossible to construct a refrigerator that, operating in a cycle, will produce no


effect other than the transfer of heat from a lower-temperature reservoir to a higher-
temperature reservoir.
2nd law of thermodynamics
Lets say that we have at our disposal two reservoirs at given temperatures

(1) What is the maximum thermal efficiency that can be achieved by an engine
operating between these two reservoirs?

(2) What are the characteristics of such an engine?

(3) Of what effect is the nature of the working substance?

CARNOT’S THEOREM
No heat engine operating between two given reservoirs can be more efficient than a
Carnot engine operating between the same two reservoirs

CARNOT’S COROLLARY
All Carnot engines operating between the same two reservoirs have the same efficiency.

CARNOT CYCLE
A Carnot cycle is a set of processes that can be performed by any thermodynamic
system whatsoever, whether hydrostatic, chemical, electrical, magnetic, or otherwise.
2nd law of thermodynamics

1.  The maximum thermal efficiency that can be achieved by a heat engine operating
between two heat reservoirs at different temperatures is the efficiency of a Carnot
engine operating between the same two reservoirs.

2. The essential characteristic of a Carnot engine is that it is reversible and


operates between two reservoirs, rather than two series of reservoirs.

3. The superior efficiency of the Carnot cycle is due to its absorbing all heat at the
highest temperature and rejecting all heat at the lowest temperature.

4. Furthermore, a Carnot engine is independent of the working substance of


the system.
2nd law of thermodynamics
An isothermal process or an adiabatic process is represented by a different curve on
each diagram.

But it is desired to formulate general principles that apply to all systems.

If we let the symbol Y denote any generalized force and the symbol X its corresponding
generalized displacement, a generalized work diagram in which Y is plotted against X
may be used to depict processes common to all systems

Work diagrams in which a generalized force such as P, is plotted against the


corresponding generalized displacement V, L, A, Z, or have been used to indicate
processes of various systems.
2nd law of thermodynamics
Consider a reversible process represented by the smooth curve i to f on the
generalized work diagram.

The dashed curves through i and f, respectively,


represent portions of adiabatic processes.

Let us draw a curve a to b, representing an


isothermal process, in such a way that the area
under the smooth curve i is equal to the area under
the zigzag sequence of processes, path iabf

Then, the work done in traversing both paths is the same


2nd law of thermodynamics
From the 1st law

But, since no heat is transferred in the two adiabatic


processes ia and bf, we have

If we are given, therefore, a reversible process in which the temperature may


change in any manner, it is always possible to find a reversible zigzag path
between the same two states, consisting of an adiabatic process followed by an
isothermal process followed by an adiabatic process, such that the heat transferred
during the isothermal segment is the same as that transferred during the
original process.
2nd law of thermodynamics
Now, consider the smooth closed curve on the generalized work diagram.

Since no two adiabatic lines can intersect,


a number of adiabatic lines may be drawn,
dividing the cycle into a number of
adjacent strips.

A zigzag closed path may now be drawn, consisting of alternate adiabatic and
isothermal portions, such that the heat transferred during all the isothermal portions is
equal to the heat transferred in the original cycle.
2nd law of thermodynamics
Consider the two isothermal processes ab and cd at the temperature T1 and T2
respectively.

During the process ab conducted at


temperature T1, heat Q1 is absorbed,
and the process cd conducted at the
temperature T2, heat Q2 is
rejected.

Since ab and cd are bounded by the


same adiabatic curves, abed is a
Carnot cycle, and we so we can write
2nd law of thermodynamics
For the sake of simplicity, we have been considering only the absolute values of heat
entering or leaving a system, thus ignoring the sign convention

Let us now return to the sign convention


and regard any Q as an algebraic symbol,
positive for heat absorbed by a system
and negative for heat rejected from a system.
We may then write

where Q1 is a positive number and


Q2 is a negative number.
2nd law of thermodynamics
Since the isothermal curves ef and gh are bounded by the same two adiabatic
curves, efgh is also a Carnot cycle

If a similar equation is written for each pair of


isothermal curves bounded by the same two
adiabatic curves and if all the equations are
added, then the result obtained is that

Since no heat is transferred during the adiabatic portions of the zigzag cycle,
we may write

where the summation is taken over the entire zigzag cycle consisting of Carnot
cycles, j in number.
2nd law of thermodynamics
Now, imagine the cycle divided into a very large number of strips by
drawing a large number of adiabatic curves close together.

If we connect these adiabatic curves


with small isothermal curves, then a
zigzag path may be traced that can
be made to approximate the original cycle
as closely as we want.

When these isothermal processes


become infinitesimal, the ratio dQ/T for an infinitesimal isothermal between
two adjacent adiabatic curves is equal to the ratio dQ/T for the infinitesimal
piece of the original cycle bounded by the same two adiabatic curves.
2nd law of thermodynamics
In the limit, therefore, for any reversible cycle, we can write

The circle through the integral sign


signifies that the integration takes place
over the complete cycle, and the letter
R emphasizes the fact that the equation
is true only for a reversible cycle.

This result, known as Clausius' theorem, is one part of Clausius' mathematical


statement of the second law.
2nd law of thermodynamics
For every infinitesimal amount of heat that enters a system during an infinitesimal
portion of a reversible process, there is an equation

It follows, therefore, that the total amount of heat transferred in a reversible


process is given by

This integral can be interpreted graphically as the area under a curve on a


diagram in which T is plotted along the y-axis and S along the x-axis, a so-
called "TS diagram.”

The shape of the curve on the TS diagram is determined by the kind of reversible
process that the system undergoes.
2nd law of thermodynamics
An isothermal process is a horizontal line
In the case of a reversible adiabatic process

Also, for an adiabatic process,

So, if T is not zero, then

and S is constant.

Therefore, during a reversible adiabatic process, the entropy


of a system remains constant, or, in other words, the system undergoes an
isentropic process.

An isentropic process on a TS diagram is obviously a vertical line, called an "isentrope.”


2nd law of thermodynamics
Other processes can also be plotted on a TS diagram. For a reversible isobaric
process, the curve has a slope,

Similarly, by imposing the condition of constant


Volume, the slope of a reversible isochoric
process is given by

The slopes are independent of the nature of the hydrostatic system, because the
requirement of constant pressure and constant volume eliminated the equation of
state of the ideal gas
2nd law of thermodynamics
Two isothermal and the two adiabatic
processes that make up any Carnot cycle form
a rectangle on a TS diagram, regardless of the

Temperature
nature of the working substance

Only reversible processes may be plotted on a


TS diagram, because of the definition of
entropy

Entropy

The TS diagram is particularly convenient for


representing all the idealized reversible cycles
for various heat engines.
2nd law of thermodynamics
The TS diagram is particularly convenient for
representing all the idealized reversible cycles
for various heat engines.

The closed curve consisting of an upper portion


R1 and a lower portion R2 represents any
reversible engine cycle that is not a
Carnot cycle.

The area under R1 (positive area) is equal to the positive heat Q1 absorbed by
the system, and the area under R2 (negative area) is equal to the negative heat
Q2 rejected by the system.

The area inside the closed curve is, therefore, Q1-Q2, or W.

The thermal efficiency of the engine is W/Q1, which may be measured directly from
the diagram.
2nd law of thermodynamics
The first part of the second law considered only reversible processes. The
second part deals with irreversible processes. For a reversible cycle

Let us consider an irreversible cycle and


calculate its closed integral.

High-temperature reservoir at T1 supplying a small quantity of heat


dQ1 to an auxiliary reversible engine R.

The purpose of R is to provide


reversible heat for the irreversible engine I.

Engine R rejects a small amount


of heat dQ at temperature T that is supplied
to the irreversible engine I.
2nd law of thermodynamics
Engine R rejects a small amount of heat dQ at temperature T that is supplied to
the irreversible engine I.

Engine I does a small amount of work dW


during an irreversible cycle, so the combined system
of engine R and engine I also performs an
irreversible cycle.

The net work of the combined system, according to


the first law, equals dQ1.

But the net work cannot be positive, according to the Kelvin-Planck


statement of the second law, since the combined system
exchanges heat with a single reservoir.

So, dQ1 cannot be positive.

Moreover, if dQ1 equals zero, then, at the end of the cycle, engine I and its
surroundings have returned to their original state. This result, however, is
contrary to the irreversibility of engine I. So, we conclude,
2nd law of thermodynamics
But the net work cannot be positive, according to the Kelvin-Planck
statement of the second law, since the combined system
exchanges heat with a single reservoir.

So, dQ1 cannot be positive.

Moreover, if dQ1 equals zero, then, at the end of the cycle,


engine I and its surroundings have returned to their original state.
This result, however, is contrary to the irreversibility of engine I.
So, we conclude,

Engine I generates heat that flows out of the system.

From the definition of the thermodynamic temperature scale,


in differential form for reversible engine R,
2nd law of thermodynamics
Integrating around a cycle,

However, T1 is the constant temperature of the reservoir, so

The heat dQ rejected from R is absorbed by I, so, dQR=dQI.

Substituting this expression and recognizing that the closed integral on the
left now applies to the irreversible system, we obtain
2nd law of thermodynamics
Since T1> 0, the result is

This equation provides the second part of the second law and is known as
the inequality of Clausius.

It states that for an internally irreversible cycle, the closed integral I dQ/T of the ratio of
the heat absorbed by a system to the temperature at which the heat is received is
always less than zero.

The closed integral is less than zero for an irreversible cycle and equal to zero for a
reversible cycle.

Combining the two equations yields Clausius' mathematical statement of the second
law:
2nd law of thermodynamics
HEAT AND ENTROPY IN IRREVERSIBLE PROCESSES

Consider a cycle in which a system begins


in an initial equilibrium state i, passes
during an irreversible process I to a final
equilibrium state f, and then returns by a
reversible process R to the initial state i,

Since entropy is a state function, its closed


integral is always zero:
2nd law of thermodynamics
Since entropy is a state function, its closed integral is always zero:

From the definition of entropy,


2nd law of thermodynamics
The term reversible adiabatic implies the term isentropic.

Isentropic, does not necessarily imply reversible adiabatic.

For an isentropic process, in general, we have

It follows that for an isentropic process, either


dQ = 0 reversible,
Or dQ < 0 irreversible.

Thus, reversible isentropic implies adiabatic, and isentropic adiabatic implies


reversible. But, irreversible isentropic is not adiabatic dQ < 0 and implies that
heat flows out of the system.
2nd law of thermodynamics
ENTROPY AND THE CRITERION FOR EQUILIBRIUM

Spontaneous process is, irreversible, and the movement of the system from its initial
non-equilibrium state to its final equilibrium state is accompanied by an increase in the
entropy of the system.

The attainment of the equilibrium state coincides with the entropy reaching a maximum
value, and hence, for such systems, entropy can be used as a criterion for determining
the equilibrium state.

In an isolated system of constant internal energy, U, and constant volume, V,


equilibrium is attained when the entropy of the system is at maximum, consistent with
the fixed values of U and V.
2nd law of thermodynamics
ENTROPY AND THE CRITERION FOR EQUILIBRIUM
Consider the chemical reaction occurring in anLAW
THE SECOND adiabatic enclosure at constant volume
OF THERMODYNAMICS

A+B=C+D

Starting with A and B, the reaction will


proceed from left to right as long as the

Entropy
entropy of the system is thereby increased; Equilibrium
or, conversely, starting with C and D, the
reaction will proceed from right to left,
again provided that the entropy of the
system is thereby increased. (A + B) Composition (C + D)

Figure 3.7 Schematic representation of the entropy of a closed system conta


A point is reached along the reaction coordinate
+ D as at which ofthe
a function theentropy of reaction
extent of the the system
A + B has
= C + D at co
its maximum value. energy and volume.

further reaction in either direction would decrease the entropy and, h


occur spontaneously. This concept will be utilized when we discuss th
gases in Chapter 11.
2nd law of thermodynamics
Suppose one wants to cool an object with a refrigerator
to a desired low temperature, that is, to lower the
temperature of a body of finite mass from the
temperature T1 of its surroundings to any desired low
temperature T2.

A refrigerator operating in a cycle between a reservoir


at T1 and the body itself is utilized, and, after several
complete cycles have been completed, a
quantity of heat Q has been removed from the body, a
quantity of work W has been supplied to the
refrigerator, and a quantity of heat Q + W has been
rejected to the reservoir
2nd law of thermodynamics
Applying the entropy principle, we obtain

Multiplying by T1 and transposing, we get

Smallest possible value for W is

The calculated value of W(min) is used to provide an estimate of the minimum cost of
operation of the refrigerator.
2nd law of thermodynamics
Dependence of entropy on temperature

Dependence of entropy on temperature can be calculated at constant volume as


follows:

δ q rev dU PdV C V
dS = = + = dT = C V d ln T
T T T T
T2
ΔSV = S2 − S1 = ∫ C V d ln T
T1

Dependence of entropy on temperature can be calculated at constant pressure as


follow:

δ q rev 1 1 1 C dT
dS = = [dU + d (PV )] = d (U + PV ) = dH = P = C P d ln T
T T T T T
T2
ΔSP = S2 − S1 = ∫ C p d ln T
T1
2nd law of thermodynamics
Volume Dependence of entropy
We know; δ q rev 1
dS = = [dU + d (PV )]
T T

and ⎛∂U⎞ ⎛∂U⎞


dU = ⎜⎜ ⎟⎟ dT + ⎜⎜ ⎟⎟ dV
⎝ ∂ T ⎠V ⎝ ∂ V ⎠T

1 ⎛∂U⎞ 1 ⎡⎛ ∂ U ⎞ ⎤
dS = ⎜⎜ ⎟⎟ dT + ⎢⎜⎜ ⎟⎟ + P ⎥ dV
So T ⎝ ∂ T ⎠V T ⎢⎣⎝ ∂ V ⎠T ⎥⎦

As S is function of state therefore the above expression forms an exact differentials.


Hence
∂ ⎡1 ⎛∂U⎞ ⎤ ∂ ⎡1 ⎛∂U⎞ P ⎤
⎢ ⎜⎜ ⎟⎟ ⎥ = ⎢ ⎜⎜ ⎟⎟ + ⎥
∂ V ⎢⎣ T ⎝ ∂ T ⎠ V ⎥⎦ ∂ T ⎢⎣ T ⎝ ∂ V ⎠T T ⎥⎦ V
T
2nd law of thermodynamics
Volume Dependence of entropy

On simplification the above expression yields:


⎛∂P⎞ ⎛∂U⎞
T ⎜⎜ ⎟⎟ = ⎜⎜ ⎟⎟ + P
⎝ ∂ T ⎠ V ⎝ ∂ V ⎠T

So we can write
1 ⎛∂U⎞ ⎛ ∂P⎞
dS = ⎜⎜ ⎟⎟ dT + ⎜⎜ ⎟⎟ dV
T ⎝ ∂ T ⎠V ⎝ ∂ T ⎠V
And under isothermal condition dT = 0 lead to the following expression:

⎛ ∂P ⎞
dS T = ⎜⎜ ⎟⎟ dV
⎝ ∂ T ⎠V
2nd law of thermodynamics
Volume Dependence of entropy
⎛ ∂P ⎞
dS T = ⎜⎜ ⎟⎟ dV
⎝ ∂ T ⎠V
⎛∂P⎞
In case of gas one can directly integrate the above expression to calculate the ⎜⎜
∂ T
⎟⎟
⎝ ⎠V
change in entropy during a process.
However, in case of solid and liquids, the equation of state is not known and
can also not be determined experimentally. Hence in such cases this partial
differential is required to be expressed in terms of some experimentally
determinable parameters. For this purpose the reciprocity theorem is used to write
the following:
⎛ ∂P⎞ ⎛∂V⎞ ⎛ ∂P ⎞
⎜⎜ ⎟⎟ = − ⎜⎜ ⎟⎟ .⎜⎜ ⎟⎟
⎝ ∂ T ⎠V ⎝ ∂ T ⎠P ⎝ ∂ V ⎠T
2nd law of thermodynamics
Volume Dependence of entropy
•  Isobaric coefficient of volumetric thermal expansion of a material (α) is
given as
1 ⎛∂V⎞
α = ⎜⎜ ⎟⎟
V ⎝ ∂ T ⎠P
•  Isothermal compressibility of a material (β) is given as
1 ⎛∂V⎞
β = − ⎜⎜ ⎟⎟
V ⎝ ∂ P ⎠T
•  So
α
dS = dV
β
Which on integration will yield the change in entropy for a change in volume
from V1 to V2 under isothermal condition
2nd law of thermodynamics
Pressure dependency of entropy
We know: δ q rev 1 P 1
dS = = dU + dV = (dU + P dV )
T T T T
From the definition of the enthalpy, one can get the total differential dH which can
be expressed as

dH = dU + P dV + VdP
1 V
dS = dH − dP
T T

⎛∂H⎞ ⎛∂H⎞
dH = ⎜⎜ ⎟⎟ dT + ⎜⎜ ⎟⎟ dP
⎝ ∂ T ⎠P ⎝ ∂ P ⎠T
2nd law of thermodynamics
Pressure dependency of entropy
After substitution, we get

1 ⎛∂H⎞ ⎡ 1 ⎛ ∂ H ⎞ V⎤
dS = ⎜⎜ ⎟⎟ dT + ⎢ ⎜⎜ ⎟⎟ − ⎥ dP
T ⎝ ∂ T ⎠P ⎢⎣ T ⎝ ∂ P ⎠ T T ⎥⎦
The equation is an exact differential because entropy being function of state.
Therefore,

∂ ⎡1 ⎛∂H⎞ ⎤ ∂ ⎡1 ⎛ ∂ H ⎞ V⎤
⎢ ⎜⎜ ⎟⎟ ⎥ = ⎢ ⎜⎜ ⎟⎟ − ⎥
∂ P ⎢⎣ T ⎝ ∂ T ⎠ P ⎥⎦ T ∂ T ⎢⎣ T ⎝ ∂ P ⎠ T T ⎥⎦ P

On simplification this yields

1 ⎡⎛∂H⎞ ⎤ ⎛∂V⎞
⎢ ⎜⎜ ⎟⎟ − V ⎥ = ⎜⎜ ⎟⎟
T ⎢⎣ ⎝ ∂ P ⎠T ⎥⎦ P ⎝ ∂ T ⎠ P
2nd law of thermodynamics
Pressure dependency of entropy
•  So after substitution we can write
1 ⎛∂H⎞ ⎛∂V⎞
dS = ⎜⎜ ⎟⎟ dT + ⎜⎜ ⎟⎟ dP
T ⎝ ∂ T ⎠P ⎝ ∂ T ⎠P

•  For an isothermal process the above expression yields,

⎛ ∂V ⎞
dST = − ⎜⎜ ⎟⎟ P dP = − α V dP
⎝ ∂T ⎠

•  On integration, one can calculate the change in entropy for a change in pressure from P1 to P2
under isothermal conditions.
2nd law of thermodynamics
Relationship between CP & CV
•  We have derived the following relationships:

⎛∂U⎞ ⎛ ∂P⎞ ⎛∂H⎞ ⎛∂V⎞


⎜⎜ ⎟⎟ = T ⎜⎜ ⎟⎟ − P ⎜⎜ ⎟⎟ = V − T ⎜⎜ ⎟⎟
⎝ ∂ P ⎠T ⎝ ∂ T ⎠P
⎝ ∂ V ⎠T ⎝ ∂ T ⎠V

⎛ ∂P⎞ ⎛∂V⎞ ⎛ ∂P ⎞
⎜⎜ ⎟⎟ = − ⎜⎜ ⎟⎟ .⎜⎜ ⎟⎟
⎝ ∂ T ⎠V ⎝ ∂ T ⎠P ⎝ ∂ V ⎠T

1 ⎛∂V⎞ 1 ⎛∂V⎞
α = ⎜⎜ ⎟⎟ β = − ⎜⎜ ⎟⎟
V ⎝ ∂ T ⎠P V ⎝ ∂ P ⎠T
2nd law of thermodynamics
•  We know the following expression
⎛ ∂U ⎞ ⎛ ∂V ⎞ ⎛ ∂V ⎞ ⎛ ∂ V ⎞ ⎡⎛ ∂ U ⎞ ⎤
C P − CV = ⎜⎜ ⎟⎟ ⎜⎜ ⎟⎟ + P ⎜⎜ ⎟⎟ = ⎜⎜ ⎟⎟ ⎢⎜⎜ ⎟⎟ + P⎥
⎝ ∂ V ⎠T ⎝ ∂T ⎠P ⎝ ∂ T ⎠ P ⎝ ∂ T ⎠ P ⎢⎣⎝ ∂ V ⎠T ⎥⎦

⎛∂U⎞
•  Elimination of from the above equation
⎜⎜ ⎟⎟
⎝ ∂ V ⎠T
leads to the relation
⎛ ∂P⎞ ⎛ ∂V ⎞
C P − C V = T ⎜⎜ ⎟⎟ ⎜⎜ ⎟⎟
⎝ ∂ T ⎠V ⎝ ∂ T ⎠P

α2 V T
•  Or CP − CV =
β
MM209 - Thermodynamics
Instructor : Aswani Yella
2nd law of thermodynamics
Combined statement of
first and second law
•  If a system is capable of doing only mechanical work the first law equation can be put as:
dU = δq – P dV. It is not exact differential. Holds true for the reversible processes.
•  The second law for the reversible process gives
dS = δq rev / T or δq = T dS
•  The two laws therefore can lead to
dU = TdS – P dV or TdS = dU + PdV
This is the combined statement of first and second law.
It includes only those terms which are state functions only and
hence is exact differential equation.
2nd law of thermodynamics
•  For irreversible process second law gives
dS > 0
Or therefore, TdS > dU + PdV

•  For a unnatural or non spontaneous process


dS < 0
Or therefore TdS < dU + P dV
Thermodynamic Potentials
•  A system by itself, in isolated state or in contact with
surrounding shall stay in equilibrium unless acted
upon by some constraints.

•  If a system tends to move as a result of being not in


equilibrium or as a result of external constraint, there
must be a driving force making the system move from
within itself or under the applied constraints.

•  This driving force is referred to as thermodynamic


potential driving the system to change to a new state.
Thermodynamic Potentials
•  Is this driving force or potential the same under all conditions of the system or it
varies from condition to condition of the system ?

•  Heat flows from higher to lower temperature. The flow is possible due to higher
thermal potential.

•  Similarly the higher pressure is the driving mechanical potential.

•  Also higher electrical voltage is driving the electrons under the influence of
electrical potential as voltage.
Thermodynamic Potentials

•  However the question remains as to what is that potential, forcing a thermodynamic


process to take place?
•  It is easy to imagine that a system with higher associated energy will be relatively
unstable as compared to the one having lower energy.
•  In other words, when a natural changes take occurs the system moves from higher to
lower energy levels or moves from higher to lower thermodynamic potentials.
•  It also means that the energy is a potential driving the system for change to occur.
•  It also means that for equilibrium to exist the potential of all the systems or sub-systems
within it must be at the same potential.
Thermodynamic Potentials

•  So far the internal energy, enthalpy and entropy have been evolved as
energy parameters but it is not yet known as to whether these act as
potential in driving a particular process?
The Driving Force
of a Chemical Reaction
•  Why does a chemical reaction take place?
•  It was believed that the energy change accompanying a
reaction can be measured directly by the enthalpy
change at constant pressure, or change in intrinsic
energy (ΔU) at constant volume.
•  The reasoning behind this would be apparent – if a
system losses energy as a result of a chemical reaction,
that reaction will take place spontaneously – and the
greater the quantity of heat lost, the greater the driving
force behind the reaction.
The Driving Force
of a Chemical Reaction (cont.)
• C (s)+ O2 (g) = CO2(g) with evolution of heat energy, i.e.
ΔH 0 = −94050 cal/mol which happens to be a driving force in this case.
298

•  2 Fe (s) + O2 (g) = 2FeO(s) and


3FeO(s) + 2 Al (l) = 2Fe(l) + Al2O3(s)
Both have negative heats of reaction at 16000C and both take place
spontaneously

•  On the other hand, if we consider the reaction;


ZnO(s) + C(s) = Zn(g) + CO (g)
0 0
Δ H 1373 = +83200 and Δ H 298 = +56800
•  This reaction will not take place at 250C but if the system is heated to
11000C, carbon will reduce zinc oxide to produce zinc metal.
The Driving Force
of a Chemical Reaction (cont.)
•  we cannot use heats of formation as a criterion of their
tendency to take place. We must therefore search for a
more consistent rule for the driving force of a reaction.
•  Consider the reaction: ZnO(s) + C(s) = Zn(g) + CO (g)
•  At 11000C, i.e above the boiling point of Zn (9070C),
the reaction will take place between phases indicated
above. At 250C, zinc is a solid (melting point 419.60C)
so that the reaction is
ZnO(s) + C(s) = Zn (s) + CO (g)
The Driving Force
of a Chemical Reaction (cont.)
•  The most obvious difference in these reactions apart
from their temperature, is the difference in the physical
state, means a difference in the state of order of a
system and consequently in the entropy of the system.

•  ΔS0 at 250C should be much less than that 11000C,


because at 11000C two molecules of gas are being
produced from two solid molecules whereas at 250C
two solid moles only produce one gaseous mole.
The Driving Force
of a Chemical Reaction (cont.)
•  A solid to gas transformation means a comparatively large entropy increase
and the following figures for the reduction of ZnO by C:
ΔS298 = 46 cal / mol deg and ΔS1373 = 68 cal / mol deg
•  Why not use entropy change of a reaction as a measure of the driving force
behind a chemical reaction?
•  The idea is immediately contradicted if we consider the formation of the
oxide of any metal:
1
Fe(s ) + O 2 (g ) = FeO (s ) , ΔS0298 = - 17 cal / deg mol
2
•  We know that this reaction is spontaneous – an oxide film forms readily on
iron at room temperature. Thus a positive entropy change is not the
criterion of a chemical reaction.
Thermodynamic Potentials

•  So far the internal energy, enthalpy and entropy have been evolved as
energy parameters but it is not yet known as to whether these act as
potential in driving a particular process?

•  For a natural process the system moves from lower to a higher entropy
level hence entropy can not be considered as a driving force.

•  Can internal energy and enthalpy qualify as potentials capable of driving


the process towards equilibrium if already at higher levels ?

•  Enthalpy also cannot be considered as a driving force under all conditions.


Thermodynamic Potentials
•  Can internal energy and enthalpy qualify as potentials capable of driving the process
towards equilibrium if already at higher levels ?

•  If internal energy and enthalpy are potential terms then changes in them will have to be
zero at equilibrium and these will have to decrease for natural changes and increase for
unnatural changes.

•  Let us therefore see if criteria can be evolved mathematically to evaluate what constitute
as thermodynamic potential and if so under what conditions?
Thermodynamic Potentials
Potentials under constant volume
and constant entropy conditions

Mathematically these conditions are expressed as


dV = 0 and dS = 0
i) TdS > dU + P dV for natural process
So under above condition we can write
dU < 0
ii) TdS = dU + P dV for the equilibrium process
So under above conditions we can write
dU = 0
iii) TdS < dU + P dV for unnatural process
So under above conditions we can write
dU > 0
Thermodynamic Potentials
•  As internal energy decreases for natural process, remains same at equilibrium
and increases for unnatural process thus fully qualifies to be called as
thermodynamic potential under the conditions of constant volume and entropy.
•  As a corollary, the internal energy must be the function of entropy and volume
can be expressed:
U = F (S, V)
Total differential of internal energy is given by

⎛∂U⎞ ⎛∂U⎞
dU = ⎜⎜ ⎟⎟ dS + ⎜⎜ ⎟⎟ dV
⎝ ∂ S ⎠V ⎝ ∂ V ⎠S
Thermodynamic Potentials

•  We know: dU = TdS – P dV ⎛∂U⎞ ⎛∂U⎞


dU = ⎜⎜ ⎟⎟ dS + ⎜⎜ ⎟⎟ dV
⎝ ∂ S ⎠V ⎝ ∂ V ⎠S
•  On comparison this leads to

⎛∂U⎞ ⎛∂U⎞
•  ⎜⎜ ⎟⎟ = T and ⎜⎜ ⎟⎟ = − P
⎝ ∂ S ⎠V ⎝ ∂ V ⎠S

•  By specifying U as function of S and V it is possible to evaluate T and P


thereby describing the system fully.
•  By describing U as a function of any other two variables, it is not possible
to describe the system fully.
Thermodynamic Potentials
Potentials under constant pressure
and constant entropy conditions

Mathematically these conditions are expressed as


dP = 0 and dS = 0
i) TdS > dU + P dV for natural process
So under above condition we can write
dU + d (PV ) < 0
Or d (U + P V) < 0
Or dH < 0
ii) TdS = dU + P dV for the equilibrium process
So under above conditions we can write
dU + d (PV ) = 0
Or dH = 0
Thermodynamic Potentials
iii) TdS < dU + P dV for unnatural process
So under above conditions we can write
dU + d (PV ) > 0
Or dH > 0
So on the whole dH > = < 0 for unnatural, equilibrium
and natural processes as the case may be.

Therefore, the term enthalpy qualifies as being called


a potential term under constant pressure and entropy
conditions.
Thermodynamic Potentials
•  Enthalpy can therefore be described mathematically as: H = F (P, S)
•  Total differential of enthalpy can be written as
⎛∂H⎞ ⎛∂H⎞
dH = ⎜⎜ ⎟⎟ dS + ⎜⎜ ⎟⎟ dP
⎝ ∂ S ⎠P ⎝ ∂ P ⎠S

•  Also by definition: dH = d (U + P V)
•  = dU + P dV + V dP
•  = T dS + V dP
•  On comparison we get

⎛∂H⎞ ⎛∂H⎞
⎜⎜ ⎟⎟ = T and ⎜⎜ ⎟⎟ = V
⎝ ∂ S ⎠P ⎝ ∂ P ⎠S
Thermodynamic Potentials

Potentials under constant volume


and constant temperature conditions

Mathematically these conditions are expressed as


dV = 0 and dT = 0

i) TdS > dU + P dV for natural process


So under above condition we can write
dU - TdS < 0
Or d ( U – T S) < 0
Let us define new mathematical term
A=U–TS
then dA < 0
Thermodynamic Potentials
ii) TdS = dU + P dV for the equilibrium process
So under above conditions we can write
d ( U – T S) = 0
Or dA = 0
iii) TdS < dU + P dV for the unnatural process
So under above conditions we can write
d ( U – T S) > 0
Or dA > 0
The newly defined function qualifies for being referred as a
potential term under constant volume and temperature
conditions
Thermodynamic Potentials
A being the function of all state variables A also
must be state function. Expressing as before
A = F (V, T)

⎛∂A⎞ ⎛∂A⎞
Total differential of A dA = ⎜⎜ ⎟⎟ dT + ⎜⎜ ⎟⎟ dV
⎝ ∂ T ⎠V ⎝ ∂ V ⎠T

•  Now A=U–TS
dA = dU – TdS – S dT
And since, TdS = dU + P dV
Therefore dA = - S dT – P dV
On comparison we get

⎛∂A⎞ ⎛∂A⎞
⎜⎜ ⎟⎟ = − S and ⎜⎜ ⎟⎟ = − P
⎝ ∂ T ⎠V ⎝ ∂ V ⎠T
Thermodynamic Potentials
This function A was first defined by Helmholtz and
therefore is known as Helmholtz free energy.
We know dA = dU – T dS
And for reversible process qrev = T dS
An therefore qrev = dU – dA
From the First law dU = qrev – W
And hence qrev = dU + W
Comparing the two equations for qrev we get
- dA = W
Or dA = - W
That the change in Helmholtz free energy in a process is equal
to the amount of work done by the system on the surrounding
or is equal to the amount of work the system is capable of doing.
Thermodynamic Potentials
Potentials under constant pressure
and constant temperature conditions

These are by far the most commonly adopted conditions in chemical and
metallurgical engineering practices. It means
dP = 0 and dT = 0

i) TdS > dU + P dV for natural process


So under above condition we can write
dU + d (P V) - TdS < 0
Or d ( U + P V– T S) < 0
Let us define new mathematical term
G = U + P V– T S
then dG < 0
Thermodynamic Potentials
ii) TdS = dU + P dV for the equilibrium process
So under above conditions we can write
d ( U + P V– T S) = 0
Or dG = 0
iii) TdS < dU + P dV for the unnatural process
So under above conditions we can write
d ( U + P V– T S) > 0
Or dG > 0

The function defined above thus qualifies for being


called as a potential term under constant pressure
and temperature conditions
Thermodynamic Potentials

G is a function of all state variable. so it is a state function.


The function G is referred to as Gibbs free energy.
Now G=U+PV–TS
And H=U+PV
Then G=H–TS
Or Δ G = Δ H – T ΔS for a finite change
Or dG = dH – T dS – SdT in differential form
At constant pressure dP = 0 and dH = q = TdS
And hence dG = - SdT
Or
⎛ dG ⎞
⎜⎜ ⎟⎟ = − S
⎝ d T ⎠P
Thermodynamic Potentials
Again dG = dH – T dS – SdT
On putting dH = dU + P dV + V dP
dG = dU + P dV + VdP – T dS – SdT
Putting in this dU + P dV = T dS
dG = T dS + V dP – T dS – S dT
= V dP – S dT
At constant temperature when dT = 0 ; dG = V dP
Or
⎛ dG ⎞
⎜⎜ ⎟⎟ = V
⎝ d P ⎠T
Thermodynamic Potentials
Since G is a state function any change in G can be
represented as
ΔG = Δ U – T ΔS + Δ (P V)
= - Wrev + Δ (P V)
The change of Gibbs free energy during a process is
equal and opposite in sign to the net reversible work
obtainable from the process occurring under
isothermal condition when corrected for change in
volume under isobaric condition.
Thermodynamic Potentials
If the state of a system is described by a func>on of two variables f(x, y) , which sa>sfies the
equa>on
df = udx + vdy,

and we wish to change the descrip>on to one involving a new func>on g(u, y) , sa>sfying a
similar equa>on in terms of du and dy, then it is necessary to define the Legendre transform
g(u,y) as

It is readily verified that g sa>sfies the equa>on

Let us use this to define new thermodynamic state func>ons.


Thermodynamic Potentials
Consider the first law of thermodynamics for a hydrosta>c system with heat expressed in terms
of temperature and entropy,

where U is a func>on characterized by V and S. Therefore, U is convenient for situa>ons


involving changes in volume and entropy. For other situa>ons, it is easier to work with different
variables involving different func>ons.

It is important to realize that no informa>on is lost in the transforma>on from one characteris>c
func>on to another. The gain is a new func>on expressed in thermodynamic coordinates
amenable to the experimental situa>on at hand.
Thermodynamic Potentials
Important thermodynamic relations
For closed and isolated systems have fixed mass and composition and the reversible
work is done against pressure.
dU = T dS - PdV
dH = T dS + V dP
dA = - S dT – P dV
dG = - S dT + V dP

These differen>al equa>ons expressing U in terms of V and S, H in terms of P and S, and so forth,
form a complete set of func>ons, based on successive Legendre transforma>ons of the four
thermodynamic variables P, V, T, and S for a hydrosta>c system.


The characteris>c func>ons U(V, S), H(P, S), A(V, T), and G(P, T) are known as thermodynamic
poten0al func0ons because they have the property that if the func>ons are expressed in terms
of the appropriate thermodynamic variables, then all the thermodynamic proper>es of a system
can be calculated by differen>a>on only.

Thermodynamic Potentials
Important thermodynamic relations

For other simple systems, such as wires, surfaces, baWeries, electrets, or paramagnets, the
thermodynamic coordinates of pressure and volume are replaced by appropriate conjugate
variables

Extensive quan>>es simply replace volume, whereas intensive quan>>es replace nega>ve
pressure.

In a simple system of a paramagne>c solid, we can define the thermodynamic variables as


follows
Thermodynamic Potentials

Criteria for thermodynamic equilibria

Differential form Finite difference form

(dU)S, V = 0 (ΔU)S, V = 0
(dH)S, P = 0 (ΔH)S, P = 0
(dA)T, V = 0 (ΔA)T, V = 0
(dG)T, P = 0 (ΔG)T, P = 0

Since it is easy to maintain temperature and pressure


constant the Gibbs free energy criteria is employed in
chemical and metallurgical processes. However, in other
areas, other criteria are also employed.
The Driving Force
of a Chemical Reaction (cont.)
• C (s)+ O2 (g) = CO2(g) with evolution of heat energy, i.e.
ΔH 0 = −94050 cal/mol which happens to be a driving force in this case.
298

•  2 Fe (s) + O2 (g) = 2FeO(s) and


3FeO(s) + 2 Al (l) = 2Fe(l) + Al2O3(s)
Both have negative heats of reaction at 16000C and both take place
spontaneously

•  On the other hand, if we consider the reaction;


ZnO(s) + C(s) = Zn(g) + CO (g)
0 0
Δ H 1373 = +83200 and Δ H 298 = +56800
•  This reaction will not take place at 250C but if the system is heated to
11000C, carbon will reduce zinc oxide to produce zinc metal.
The Driving Force
of a Chemical Reaction (cont.)
•  A solid to gas transformation means a comparatively large entropy increase
and the following figures for the reduction of ZnO by C:
ΔS298 = 46 cal / mol deg and ΔS1373 = 68 cal / mol deg
•  Why not use entropy change of a reaction as a measure of the driving force
behind a chemical reaction?
•  The idea is immediately contradicted if we consider the formation of the
oxide of any metal:
1
Fe(s ) + O 2 (g ) = FeO (s ) , ΔS0298 = - 17 cal / deg mol
2
•  We know that this reaction is spontaneous – an oxide film forms readily on
iron at room temperature. Thus a positive entropy change is not the
criterion of a chemical reaction.
The Driving Force
of a Chemical Reaction (cont.)
•  The Second Law of thermodynamics states that a
spontaneous process is always accompanied by an
increase in entropy of the system and its surroundings.
•  The surroundings receive a quantity of heat - ΔH at
constant temperature and pressure
− ΔH
∴entropy increase of the surroundings =
T
•  If ΔS is the entropy change of the system, total entropy
change of the system and surroundings = ΔS – ΔH
T

•  For the 2nd Law to be obeyed (ΔS - ΔH ) must be +ve


T
TΔS - ΔH
= + ve
T
The Driving Force
of a Chemical Reaction (cont.)
•  we can say that (ΔH – T ΔS) must always be –ve for a reaction to proceed
spontaneously in order that the total entropy change of the system and
surroundings can be +ve, when the reaction proceeds.
•  We should examine the factor (ΔH – T ΔS) for the above three reactions in
question. For the reduction of ZnO by C at 250C
ΔH 298 - TΔS298 = 56800 -298(46) = +43100 cal / deg mol
•  The reaction cannot proceed because this factor is +ve, and the total entropy
change of the system and its surroundings is –ve
at 11000 C ΔH1373 - TΔS1373 = 83300 -1373(68) = - 10200 cal

•  This is negative so that the reaction will take place spontaneously at 11000C.
This explains why zinc oxide smelting must be carried out at temperature of the
order of 11000C in order that reduction of the oxide by carbon can proceed.
The Driving Force
of a Chemical Reaction (cont.)
•  For the oxidation of iron at 250C
ΔH 298 − TΔS 298 = − 63200 − 298(− 17 )= − 57140 cal.

•  Again it is negative, and the reaction takes place


spontaneously at 250C.
Consistent Rule
•  The driving force of a reaction can be calculated as (ΔH
- TΔS); the more negative this factor, the greater the
driving force and if the factor is +ve, the reaction will
not proceed spontaneously.
•  ΔG = ΔH - TΔS called Gibbs Free energy
The Driving Force
of a Chemical Reaction (cont.)
•  It is the maximum work available from a system at constant
pressure other than that due to a volume change. Most
metallurgical processes work at constant pressure.

•  We had already seen the fundamental importance of the


factor (ΔH-TΔS), so that ΔG is a measure of the driving
force behind a chemical reaction. For a spontaneous
change in the system, ΔG must be negative, the more
negative, the greater the driving force.
Chemical Potential
•  The general equation for the free energy change of a system with
temperature and pressure dG = VdP – SdT, does not take into account any
variation in free energy due to concentration changes.
•  We know Gʹ = Gʹ(T , P, n1 , n2 , ....)
•  From the fundamentals of partial differentiation we have
⎛ ∂Gʹ ⎞ ⎛ ∂Gʹ ⎞ ⎛ ∂Gʹ ⎞ ⎛ ∂Gʹ ⎞
dGʹ = ⎜ ⎟ dT + ⎜ ⎟ dP + ⎜⎜ ⎟⎟ dn1 + ⎜⎜ ⎟⎟ dn2 + ......
⎝ ∂T ⎠ P ,ni ⎝ ∂P ⎠T ,ni ⎝ ∂n1 ⎠Texcept
, P , n2 ....
n1
⎝ ∂n2 ⎠T , P ,n1 ....
except n2

∂G '
= S'.dT + V' dP + ∑ dn i
∂n i T , P , n1 ....
except n i

•  The coefficient ⎛ ∂Gʹ ⎞ called the chemical potential and is


⎜⎜ ⎟⎟
denoted by µ hence⎝ ∂ni ⎠except
P ,T , n1 .......
n i
Chemical Potential
⎛ ∂Gʹ ⎞
⎜⎜ ⎟⎟ = µi
⎝ ∂ni ⎠TExcept
, P , n1 .....
ni

µ is an intensive variable
This gives a new sets of fundamental equations for the open systems.

dGʹ = − S ʹdT +V ʹdP + ∑ µ i dni

dAʹ = − S ʹdT − PdV ʹ + ∑ µ i dni

dH ʹ = TdS ʹ +V ʹdP + ∑ µ i dni

dU ʹ = TdS ʹ − PdV ʹ + ∑ µ i dni


Physical Meaning of Chemical potential
•  Consider the change in free energy (dG/) of a system produced by the
addition of dnA mole of component A at constant pressure and temperature.
The change in free energy of a system is given by dG ʹ = µ A dn A = G A dn A
is the partial molar free energy of component A in solution

⎛ ∂G ʹ ⎞
G A = ⎜⎜ ⎟⎟ = µ A for a large quantity of solution
⎝ ∂n A ⎠ P ,T , n B
⎛ ∂G ⎞
G A = ⎜⎜ ⎟⎟ = µ A for one mole of solution
⎝ ∂n A ⎠ P ,T , n B
•  Chemical potential of either 1 g mol or 1 g atom of a substance dissolved in
a solution of definite concentration is the partial molar free energy. Thus
Maxwell s equations

From the properties of the exact differential


⎛ ∂M ⎞ ⎛ ∂N ⎞
equation: dZ = M dX + N dY, ⎜⎜ ⎟⎟ = ⎜ ⎟
⎝ ∂y ⎠ X ⎝ ∂x ⎠ Y
⎛ ∂T ⎞ ⎛∂P⎞
⎜⎜ ⎟⎟ = − ⎜⎜ ⎟⎟
⎝ ∂ V ⎠S ⎝ ∂ S ⎠V
⎛∂T ⎞ ⎛∂V⎞
⎜⎜ ⎟⎟ = ⎜⎜ ⎟⎟
Maxwell s relations are used
⎝ ∂ P ⎠S ⎝ ∂ S ⎠ P
frequently in thermodynamics
⎛ ∂S ⎞ ⎛∂P⎞
⎜⎜ ⎟⎟ = ⎜⎜ ⎟⎟ for the calculation of changes in
⎝ ∂ V ⎠T ⎝ ∂ T ⎠ V
thermodynamic variables for
⎛ ∂S ⎞ ⎛∂V⎞
⎜⎜ ⎟⎟ = − ⎜⎜ ⎟⎟ different processes.
⎝ ∂ P ⎠T ⎝ ∂ T ⎠P
Thermodynamic Mnemonic Square

In order to memorize important thermodynamic relationship


involving the different thermodynamic potentials Max Born
suggested a diagram known as Thermodynamic Mnemonic
Square. T
V A
•  Four sides of the square are leveled
in alphabetical order starting from the
top and moving in clock-wise direction
with four thermodynamic potentials
U G
namely A, G, H, U.

S H P

•  The other four primary functions namely V, T, P, S are placed at the four corners in such a way that
each thermodynamic potential is surrounded by the condition under which it acts
We can write the total differentials of each of
potentials with help of this diagram as follows:
–  Differential of any potential is equal to the sum of the differentials of its
adjoining variables with their coefficients equal to diagonally opposite
variables.

–  This coefficients are taken to be positive if arrow points away from the
variable and negative if it points towards the variable.

dG = - S dT + V dP
Maxwell s relations can also be read from the
diagram as follows:
–  It is required to consider the corners only
–  The square is rotated in anti clock-wise direction in such a way that the
function whose partial differential is to be arrived it appears on the top
left hand corner of the square.
–  The partial derivative of this variable w.r. t variable on the bottom left
hand corner keeping the lower right hand corner variable as constant is
equal to the partial derivative of the top right hand corner variable w.r.t
bottom right hand corner variable with bottom left hand corner variable
as constant.
–  Negative sign on the right hand side of the equation is put if the arrows
are placed unsymmetrically with respect to vertical axis drawn from
centre of the square on rotation.

⎛ ∂T ⎞ ⎛∂P⎞
⎜⎜ ⎟⎟ = − ⎜⎜ ⎟⎟
⎝ ∂ V ⎠S ⎝ ∂ S ⎠V
Standard state of free energy

Standard state is pure element or compound at 1


atm pressure and at its stablest state at the
temperature under consideration.

Free energy change of the reaction are generally


calculated when the reactants and products are
present in their standard states is called the standard
free energy change.

The standard free energy is designated by ΔG0T.

Like enthalpy, we cannot measure the absolute


value of free energy but change in free energy is
quite possible to measure.
•  Therefore, there must be some reference point
with respect to which the actual values of
various substance can be calculated.
•  The free energies of stable form of the elements
at 298 K and 1 atm pressure are arbitrarily
assigned as zero value.
•  The free energy of formation of compound are
calculated on the basis of the above
assumption and the value is described as
standard free energy of formation.
•  This quantity is generally reported at 298 K and for compound say MO, it
would be written as ΔG0298, MO.
•  The Hess s law is applicable for calculation of free energy change as it is a
state property.
•  The standard free energy of formation of compound and the standard free
energy of compound are same.
M + ½ O2 = MO 0
0
ΔG0298 = G0298,MO - G0298,M - ½ G0298, O2
ΔG0298,MO = G0298,MO
For the reaction
a A+ bB → cC + d D
the s tan dard free energy change ΔG 0 at 298 K is given by

ΔG 0298 = ∑ G 0298, Pr oduct − ∑ G 0298, Re ac tan t


= c G 0298, C + d G 0298, D − a G 0298, A − b G 0298, B

inorder to calculate the s tan dard free energy change of a reaction


the s tan dard free energies of reac tan t and products must be known
Some thermodynamic
relationships
By definition G = H – TS = U + PV –TS
differentiating dG =dU + PdV + VdP – TdS – S.dT (1)
Assuming a reversible process involving work due only to
expansion at constant pressure
According to First Law: dU = dq – PdV and from Second
Law: dq = TdS
∴dU = TdS – PdV (2)
From (1) and (2) we get dG = (TdS – PdV) + PdV + VdP
– TdS
– SdT
or dG = VdP – SdT (3)
Some thermodynamic
relationships
⎛ δG ⎞
At constant pressure, dP = 0, so that ⎜ ⎟= - S
⎝ δT ⎠ P
and at constant temperature, dT = 0 and ∴dG = VdP

RT
from PV = RT for ideal gas, dG = dP
P
Integrating between the limits PA and PB at constant
Temperature PB
dP P B
ΔG = G B − G A = RT ∫ = RT ln (4)
PA
P PA
if GA is the free energy of the system in its initial state and GB
the free energy in its final state when the system undergoes a
change at constant pressure
Some thermodynamic relationships

dGA = −S A .dT and dGB = −S B dT


d (G B -GA )= (SB - SA )dT
but ΔG = GB – GA and ΔS = SB – SA and so that d (ΔG) = -ΔS.dT

⎡ δΔG ⎤
⎢ δT ⎥ = −ΔS
⎣ ⎦P

on substitution
⎡ δ (ΔG )⎤
ΔG = ΔH − TΔS = ΔH + ⎢ ⎥
⎣ δT ⎦ P ,T

known on Gibbs – Helmholtz equa5on


Calculation of ΔG0 at high temperature

It is possible to calculate ΔG0 of a reaction at high


temperature from the ΔH0 and ΔS0 values at 298 K
(available in the literature ) in this way

ΔG 0T = ΔH 0T − T ΔS0T
T T
⎡ 0 ⎤ ⎡ 0 ΔC P ⎤
or ΔG 0T = ⎢ΔH 298 + ∫298 ΔC P dT ⎥⎦ − T ⎢ΔS 298 + ∫ dT ⎥
⎣ ⎣ 298
T ⎦
It must be remembered that if any transformation
takes place between 298 and T K in reactants and
products must be introduced in the above equation.
the temperature of a closed system of fixed ⎛composition
δqrev ⎞ is increased
⎛ dH ⎞ c p dT
Third law of Thermodynamics
dS = ⎜ per
2 at constant pressure, the increase in the entropy ⎟ =
mole =
⎜of the⎟system,
⎝ T ⎠P ⎝ T ⎠P T
by
and thus, if the temperature of a closed system of fixed composition is inc
Enunciation of third law
T
cp

2
∆S from
= S(TT, Pto) −T S(atT constant
21 , P ) = pressure,
2 1 dT the increase in the entropy per mole of the s
(6.12)
The change in entropy with constant pressure
T1 T and constant volume is given by following
Δ
equations
S , is given by
CP
of entropy is obtained as thedT
dS = area under a plot of c p /T versus T between T2
cp
T ∆Sa plot
and T 1 , or, equivalently, as the area under
T 2 and lnT 1 . Generally,
CV
and dS = S T , the
= S(T − S(T1,lnT
of2 ,cPp )versus P) =
dT molar entropy of the system at any tem-
between dT
T1 T ∫
T
is given by
This
Integration of thischange of entropy
leads to the followingis obtained as the area under a plot of c p /T versus T b
HEAT CAPACITY, ENTHALPY,
the limits T 2 andENTROPY 173
TT 1 , or, equivalently, as the area under a plot of c p versus lnT b
cp
S
the limits
T = S
lnT +

0 2 and lnT (6.13) of the system at an
dT1 . Generally, S T , the molar entropy
T the system at 0 K. In turn, the Gibbs free energy
0 of
where S is the molar entropy
perature T , is given by
0
can be written as
where S0 is the molar entropy of the system at 0 K.
T
cp

T T
cp
∆G =

0
cP dT − T

0 T
ST −=TSS00
dT +
0 T
dT

Clearly, if the entropy at 0 K is known, the thermodynamics of the reaction is com-


If the entropy at 0 K is known, the thermodynamics of the reac>on is completely known
pletely known. This was proposed by Le Chatelier in 1888:

It is highly probable that the constant of integration is a determinate function of certain


Third law of Thermodynamics
if the value of S0 for a reac>on could be determined, ΔG would be known as a func>on of
temperature as well, and hence, the reac>on thermodynamics would be known.

•  These equations also state that for calculation of absolute value of entropy of any
substance, these constants should be known.

•  In order to evaluate the constant, Nernst analyzed the low temperature data on free
energy and enthalpy of chemical reactions.

•  The analysis lead to the formulation of first, the Nernst heat theorem and later the
third law of thermodynamics.
Third law of Thermodynamics
Nernst heat theorem
•  Nernst collected enthalpy of
formation of various reactions
by calorimetric method and
determined free energies as a
function of temperature by emf
method.

•  These free energies and


enthalpy when plotted against
temperature yielded curves as
shown.
Third law of Thermodynamics
It is seen from the figure that at low temperature that both
enthalpy and free energy of a reaction approaches each
other asymptotically with the asymptote
174 laying parallel to TO THE THERMODYNAMICS OF MATERIALS, SIXT
INTRODUCTION
temperature axis. This lead Nernst to arrive at the following
conclusions: ∂ (Δ G )
(i ) Lim =0
T →0 ∂T
DHa®b
∂ (Δ H )
(ii) Lim =0
T →0 ∂T
As
⎡ ∂ (Δ G )⎤ DH(T1) Slope = –DSa®b
⎢ ∂ T ⎥ = − ΔS
⎣ ⎦P DGa®b

T1 T®
Therefore, one can write Lim Δ S = 0 Ga = Gb
T →0
Third law of Thermodynamics
Statement of Nernst heat theorem
It states that both entropy change and temperature
coefficients of enthalpy and free energy changes for the
reaction tends to zero as temperature approaches 0 0K.
Entropy of a pure substance
A pure substance is a pure element or pure compound.
Consider the formation of compound AB from elements A
and B i.e
A(s) + B(s) = AB(s)
For which ΔS0 = S0AB - S0A - S0B
At absolute zero temperature ΔS0 = 0 it is possible provided
0 0 0
either i) SAB = (SA + SB )

Or ii) S0AB , S0A and S0B are all individually zero


Third law of Thermodynamics

•  From a probability point of view, the first alternative is very unlikely as a general
feature. It may be true, by chance, in a few cases.

•  Hence alternative (ii) is accepted as of general validity and it may be concluded that
entropies of pure solids at T = 0 are zero

•  Therefore, the absolute value of entropy of a pure substance at any temperature can
be determined by taking T = 0, S = 0 as the lower limit.
Third law of Thermodynamics

Various statements of third law


All reactions involving substances in the condensed state ΔS is zero at absolute zero

The entropy of any homogeneous crystalline substance which is in complete internal


equilibrium may be taken as zero at 0 0K

The entropy of any phase whose quantum states and atomic arrangement corresponds
to a unique lowest energy state at the absolute zero is zero
Third law of Thermodynamics

Experimental verification
of the third law

•  Third law is not so obvious as first and second law; hence it is required to describe
some of the evidence by which it was established.

•  The so called direct verification of the third law involves the application of the
second law, namely the principle that the entropy of the system is a function of state
and the net entropy change experienced by a system undergoing a cycle is therefore
zero.
Third law of Thermodynamics
•  Let us consider the cycle shown T
in the figure.
II
•  The starting point is a system
composed of reactants at the
absolute zero. 0K
•  The first step of the cycle
I
consists in heating the reactants III
to temperature T.
•  The reaction is allowed to
completion at T in the second
step. IV
•  The products are cooled to 0
0 % reacted 100
absolute zero in the third step.
•  The fourth step which imaginary,
the reverse reaction is allowed to
proceed
∆SII = −(∆SI + ∆SIII )

Third law of Thermodynamics


where:

Ttrans
c p(α )
•  We have from the second law ∆SI =

0 T
dT

ΔSI + ΔSII + ΔSIII + ΔSIV = 0 ∆H trans


∆SII = = H (β, Ttrans ) − H (α, Ttrans )
Or ΔSIV = - (ΔSI + ΔSII + ΔSIII ) Ttrans
0
c p (β )
•  ∆S =
Since the entropy change in the first three steps measured
III
Ttrans ∫ dT
experimentally,
T
the
entropy change at absolute zero can be determined.
•  Let us consider the following transformation reaction DSII
Ttrans

DSI DSIII

0K
DSIV

a b
HEAT CAPACITY, ENTHALPY, ENTROPY
∫0 T
177
∆H trans
∆SII =
= H (β, Ttrans ) − H (α, Ttrans )
Third law of Thermodynamics
6.6 EXPERIMENTAL VERIFICATION OF THE THIRD
Ttrans
0 LAW
c p (β )
∆SIII =
Ttrans T ∫
dT
The Third Law can be verified by considering the phase transition of one mole
•  The Third Law can be verified by considering the phase transi>on of one mole of
of an element, such as
an element, such as DSII
α→β α →β Ttrans

where α and β are allotropes of the element


where α and β are allotropes of the element. In Figure 6.11, T trans is the temperature,
•  at Tatmospheric pressure, at which the α and β phases are in equilibrium with one
trans is the temperature, at atmospheric pressure,
another. For the cycle shown in Figure 6.11,
at which the α and β phases are in equilibrium
DSI DSIII
with one another. ∆SIV = ∆SI + ∆SII + ∆SIII

•  ForFor the cycle shown


the Third Law to be obeyed, ∆ S IV = 0, which requires that
∆SIV = ∆SI + ∆SII + ∆SIII
∆SII = −(∆SI + ∆SIII )
0K
For the Third Law to be obeyed, ∆SIV = 0,
•  where: DSIV

which requires that ∆SII = −(∆SI + ∆SIII )


Ttrans
a b
c p(α )
∆SI =
∫ 0 T
dT
Figure 6.11 The cycle used for the experimental verification of the Th
∆H trans Thermodynamics.
∆SII = = H (β, Ttrans ) − H (α, Ttrans )
Ttrans
0
c p (β )
∆SIII =
∫ Ttrans T
dT
∫0 T
∆H trans
∆SII = = H (β, Ttrans ) − H (α, Ttrans )
Third law of Thermodynamics Ttrans
0
c p (β )
∆SIII =
∫ Ttrans T
dT
The cycle shown has been examined for the case of
sulfur, which has two allotropes:
DSII
a monoclinic form which is stable above 368.5 K Ttrans
an orthorhombic form which is stable below 368.5 K

The molar enthalpy of transforma>on is 400 J/mole at
the equilibrium transforma>on temperature of 368.5 K
DSI DSIII

Since monoclinic sulfur can be supercooled with rela>ve ease,


the varia>ons, with temperature, of the heat capaci>es of both
allotropes have been measured experimentally at
temperatures below 368.5 K 0K
DSIV

a b

Figure 6.11 The cycle used for the experimental verification of the Th
Thermodynamics.
∫ 0 T
∆H trans
is called the experimental entropy change , and – (∆ S I + ∆ S III ) is ∆ SII = the = H (β, Ttrans ) − H (α, Ttrans )
Third law of Thermodynamics called
aw entropy change . If the Third Law is valid, ∆ S II = – (∆ S I + ∆ S III ).
Ttrans
0
c p (β )
cycle shown in Figure 6.11 has been examined for the case of sulfur,
allotropes:
∆SIIIwhich
a monoclinic form which is stable above 368.5 K and an ortho-
=

Ttrans T
dT
Since monoclinic sulfur can be super-cooled with rela>ve ease, the varia>ons, with temperature,
c form of the heat capaci>es of both allotropes have been measured experimentally at temperatures
which is stable below 368.5 K, with a molar enthalpy of transforma-
400 J/mole at the equilibrium transformation temperature of 368.5 K. Since DSII
below 368.5 K
inic sulfur can be supercooled with relative ease, the variations,Ttrans
with temper-
f the heat capacities of both allotropes have been measured experimentally at
atures below 368.5 K. The measured heat capacities give
The measured heat capaci>es give
368.5
c p( rhombic )
∆SI =
0 ∫ T
dT = 36.86 J/K DSI DSIII

∆H trans 400
∆SII = = = 1.09 J/K
Ttrans 368.5

0K
DSIV
0
c p( monoclinic )
∆SIII

368.5 T
dT = −37.8 J/K
a b

Figure 6.11 The cycle used for the experimental verification of the Th
Thermodynamics.
( ∆SI + ∆SIII ) = − ( 36.86 − 37.8 ) = 0.94 J/K
s is the value of the Third Law entropy change. The value of was shown to be 1.09 J/K
The value of the experimental entropy change ∆S the experimen-
II
opy change ∆SII was shown to be 1.09 J/K. Since the difference between the
Third law of Thermodynamics
Consequences of the third law
Third law leads to following important consequences
1.  CP, CV and α will be zero at absolute zero.
G=H−TS
⎛∂G ⎞ ⎛∂H⎞ ⎛ ∂S ⎞
⎜⎜ ⎟⎟ = ⎜⎜ ⎟⎟ − T ⎜⎜ ⎟⎟ − S
⎝ ∂ T ⎠P ⎝ ∂ T ⎠P ⎝ ∂ T ⎠P
⎛∂G ⎞ ⎛∂H⎞
As we know ⎜⎜ ⎟⎟ = − S and ⎜⎜ ⎟⎟ = C P
⎝ ∂ T ⎠P ⎝ ∂ T ⎠P
⎛ ∂S ⎞
we can write C P = T ⎜⎜ ⎟⎟
⎝ ∂ T ⎠P
⎛ ∂S ⎞ Prove that CV is zero
as ⎜⎜ ⎟⎟ is finite , at T = 0 ⇒ C P = 0
⎝ ∂ T ⎠P at absolute zero
Third law of Thermodynamics
1 ⎛ ∂V⎞
α = ⎜⎜ ⎟⎟
V ⎝ ∂ T ⎠P
according to max well' s equation
⎛ ∂V⎞ ⎛ ∂S ⎞
⎜⎜ ⎟⎟ = − ⎜⎜ ⎟⎟
⎝ ∂ T ⎠P ⎝ ∂ P ⎠T
⎛ ∂S ⎞
as T → 0 , S → 0 so ⎜⎜ ⎟⎟ =0
⎝ ∂ P ⎠ T →0
⎛ ∂V⎞
⇒ ⎜⎜ ⎟⎟ = 0 ⇒ α = 0
⎝ ∂ T ⎠P
Third law of Thermodynamics
2.  Unattainability of absolute zero temperature
let us consider a carnot cycle in which heat is absorbed at temperature T (T > 00K)
delivered to cold reservoir maintained at 00K. Entropy change during such a cycle will
be equal to zero i. e.
ΔSI + ΔSIII = 0

where ΔSI is the entropy change during isothermal expansion and ΔSIII is the entropy
change during isothermal compression.
Third law of Thermodynamics
According to third law the entropy change during isothermal
volume change (ΔSIII ) at 00K is zero. Hence ΔSI will be zero.

But this not true as both heat exchange and temperature for
this is finite non-zero and positive.

Hence one cannot design a cycle in which the temperature of


the working substance descend to the absolute zero.

Thus it can be concluded that the temperature of 00K cannot


be attained.
Third law of Thermodynamics
3.  Calculation of entropy and free energy from calorimetric data.
Entropy of a substance at constant volume is given by
T
SV = ∫ C V d ln T + S0,V
0

As per third law S0,V = 0


T
therefore, SV = ∫ C V d ln T
0
From the knowledge of heat capacity which can be
determined by calorimetric techniques, one can
calculate the absolute value of entropy of a component
at any temperature T.
Third law of Thermodynamics
Third law also helps in the calculation of free energy during the
chemical reaction from the calorimetric data obtained in the
form of enthalpy of a reaction as a function of temperature. We
know ΔG = ΔH – T ΔS
T T
ΔCP
ΔS = ∫ d T and ΔH = ΔH 0 + ∫ ΔCP d T
0
T 0

Where ΔH0 is the enthalpy of reaction at 00K.


T T
Or ΔC P
ΔG = ΔH 0 + ∫ ΔC P d T − T ∫ dT
0 0
T
All the quantities present in the above expression can be
determined by calorimetric techniques. Thus, one can calculate
the change in free energy of any reaction at desired temperature