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Thermodynamics - Lectures b4 Midsem
Thermodynamics - Lectures b4 Midsem
Some are spontaneous processes that occur in nature and some are non-
spontaneous in nature but we cause them to occur
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
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
First step to define a free body, then identify all forces exerted on it
Once the system is defined and relevant interactions with other systems
are identified.
• 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.
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
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.
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.
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
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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.
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
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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
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lar animation
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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.
er 1 Getting Started
Air
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reinforce many
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these anima-
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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
THEROMODYNAMIC SYSTEMS
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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
• The minimum number of variable required to describe the state of the system
are called independent state variables.
Introduction
• All other variables whose values get fixed with the specification of
independent state variables are referred to as dependent state variables.
Intensive Extensive
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
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
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
The ratio of the extensive property to the mass is called the specific
value of that property
The molar properties are defined as the ratios of the properties to the
mole number (N) of the substance
At a given state, each property has a definite value that can be assigned
without knowledge of how the system arrived at that state.
Thermodynamics also deals with quantities that are not properties, such
as mass flow rates and energy transfers by work and heat.
Introduction
Process
When any of the properties of a system changes, the state changes and
the system is said to undergo a process
Process System
System
lsoBARlc
Fis.12 -
Sc he matic tion of
re Pre s e nta
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
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.
• 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,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
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
∆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
⎛ ∂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
⎛ ∂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 ⎥⎦
In thermodynamics, the concept is more far-reaching, including not only a balance of forces
but also a balance of other influences.
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
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
Stable Equilibrium
If ball is moved from its position it will roll off the hill, until it
finds a stable point
Unstable Equilibrium
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
H2O vapors
H2O vapors H2 + O2
H2O liquid
Thermodynamic reversibility
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
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
Liquid
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.
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
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 Celsius temperature scale uses the unit degree Celsius (8C), which has the same magnitude
as the kelvin
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
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
Hydrostatic system: Closed cylinder equipped with a frictionless movable piston on which the
system and the surroundings may act.
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
The presence of minus sign before PdV ensures that a negative dV gives rise to positive work
done on 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
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
The capacity represents a combination of an effort and the change brought about by the effort.
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
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
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
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
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
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
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
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
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
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
• 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
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
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
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 separates heat and work interactions between the system and surroundings as two different
terms.
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
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
As both Q and Tf-Ti become smaller, this ratio approaches a limiting value known as the
heat capacity denoted by C
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
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
Similarly, the heat capacity at constant volume is the result while volume is held constant
Cv is a function of V and T
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 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
= M dP + N dV (Say)
Enthalpy
⎡ ⎛ ∂U ⎞ ⎤ ⎡ ⎛ ∂U ⎞ ⎤
M = ⎢V + ⎜ ⎟ ⎥ , N = ⎢P + ⎜ ⎟ ⎥
⎣ ⎝ ∂ P ⎠V ⎦ ⎣ ⎝ ∂V ⎠P ⎦
⎛∂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 ⎞
⎜⎜ ⎟⎟ = ⎜⎜ ⎟⎟ = 0
⎝ ∂ P ⎠T ⎝ ∂ P ⎠T
• 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
dH = dq + VdP
At a constant Pressure dP =0
And we know ⎛ ∂U ⎞ ⎛ ∂U ⎞
dU = ⎜⎜ ⎟⎟ dV + ⎜⎜ ⎟⎟ dT
⎝ ∂ V ⎠T ⎝ ∂ T ⎠V
⎛ ∂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
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
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
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
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
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.
pi, Vi, Ti
During this process the pressure is Pi and volume changes pi pf
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
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
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.
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
Or T f V f γ −1 = Ti Vi γ −1 where CP
γ =
CV
Or TV γ −1
= Const Or
PV γ = Const
P V γ = m = a const.
Polytropic Process
⎛ 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
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
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
hν
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
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
CaF2(l)
100 a-CaF2
a-CaC
0
300 500 700 900 1100 1300 1500
Temperature, K
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.
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
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)
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
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:
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:
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
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
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
∆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)
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
Enthalpy, H, kJ
Pb (s) b
298 a
0
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
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
∫
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
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
∫
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)
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 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
• If the initial state is not in equilibrium with surroundings → left to itself → it will
spontaneously move towards equilibrium.
• 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
Hot object → Decrease in internal energy of the body and increase in internal
energy of surroundings.
Internal energy of surroundings would not decreases spontaneously and warm the
body.
to its initial temperature.
(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
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.
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
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
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 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”
(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.
• 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
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
of the cylinder.
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 _gA
8 :AA
b\dA: ) YA !bgpYA
\2 p
A
A !d
A\QY gJ YA
ndp\gdu \ AAd pg\)_A46 Y! :
\dQ Y\ Ap!d\gd YA p\gd
2 law of thermodynamics Introduction to the Thermodynamics of Materials
gA
Ygg \ _\b!A pg\\gd8 YAd :
gp3.5)A_g AN ILLUSTRATION \8 !d: !JA
gbA
OF IRREVERSIBLE g2\__!
AND REVERSIBLE
PROCESSES
A_A :gd g \ Kd!_ pg\\gdu rYAYA
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 more nearly equal
are the two work terms, and in the limit that they are
equal, no permanent change uinYA
occurs p
A
A \dFigure
the external YA3.2Q! \d YA p\gd r!s \ :AA
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
! \
AbgA:
water vapor. YA Q! Ap!d: ::Ad_ !d:
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
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
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
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.
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.
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
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
<.,-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 R
~
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
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
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
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
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
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
Hence, points to the left of 2 cannot be reached from point 1 by way of any adiabatic
path.
Consider an adiabatic path from point 1 to point 2a that is also located onandthe
The First isothermal
Second Laws of Thermodynamics 69
θ2.
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
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.
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
But it is still possible to identify reversible adiabatic paths for which the equality dqrev = 0
is satisfied
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
1 i
States on surface S2, cannot be connected to states on The First and Second Laws of Thermodynamics
r:v I
69
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
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.
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.
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.
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
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
<.,-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 R
~
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).
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
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
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
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
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
Hence, points to the left of 2 cannot be reached from point 1 by way of any adiabatic
path.
Consider an adiabatic path from point 1 to point 2a that is also located onandthe
The First isothermal
Second Laws of Thermodynamics 69
θ2.
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
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
But it is still possible to identify reversible adiabatic paths for which the equality dqrev = 0
is satisfied
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
1 i
States on surface S2, cannot be connected to states on The First and Second Laws of Thermodynamics
r:v I
69
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
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.
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.
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.
irreversibly is 2ΔPV.
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 _gA
8 :AA
b\dA: ) YA !bgpYA
\2 p
A
A !d
A\QY gJ YAndp\gdu \ AAd pg\)_A46 Y!
2 law of thermodynamics :
\dQ Y\ Ap!d\gd YA p\gd
Introduction to the Thermodynamics of Materials
gA
Ygg \ _\b!A pg\\gd8 YAd :
gp3.5)A_g AN ILLUSTRATION \8 !d: !JA
gbA
OF IRREVERSIBLE g2\__!
AND REVERSIBLE
PROCESSES
A_A :gd g \ Kd!_ pg\\gdu rYAYA
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
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.
Thus,
Forfor a reversiblecondensation
a reversible condensation
and
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
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
(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
consider the free expansion (i.e., expansion against zero atmospheric pressure) of 1
mole of an ideal gas from VA to VB.
The final state of the free expansion is the same as the state of the isothermal
reversible expansion process
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.
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
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 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
I
dS-~
.
V1
CvdT
•SqrevExpansion:
Calculation of ΔS for the Reversible Adiabatic
Calculation of AS T
T for the Reversible Adiabatic Expansion
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
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
.,..
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.
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.
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
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
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
Work, w
Work, w
∆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
Applying the first law to one complete cycle, remembering that there is no change of
internal energy, we get
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.
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.
Therefore, the refrigerator and heat engine together constitute a violation of the Kelvin-
Planck statement.
2nd law of thermodynamics
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.
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.
(1) What is the maximum thermal efficiency that can be achieved by an engine
operating between these two reservoirs?
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 .
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.
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.
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.
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:
During the isothermal vaporization 2 to 3, heat QH is absorbed from the hotter reservoir
at TH .
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
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.
1. Absorbs heat QH from the high- 1. Absorbs heat QH’ from the high-
temperature reservoir. temperature reservoir.
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.
which is positive.
Consider two Carnot engines R1 and R2, operating between the same two reservoirs.
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.
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.
The Carnot engine provides the basis for the thermodynamic temperature scale.
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
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
So, the Carnot engine supplies the universality that is lacking in the ideal-gas
temperature scale.
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.
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
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.
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.
If θ1 and T1 refer to any temperature, and θ2 and T2 refer to the triple point of
water, then
(1) What is the maximum thermal efficiency that can be achieved by an engine
operating between these two reservoirs?
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.
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.
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
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.
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.
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
and S is constant.
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
Entropy
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 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
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.
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
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.
A+B=C+D
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)
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
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
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
1 ⎛∂U⎞ 1 ⎡⎛ ∂ U ⎞ ⎤
dS = ⎜⎜ ⎟⎟ dT + ⎢⎜⎜ ⎟⎟ + P ⎥ dV
So T ⎝ ∂ T ⎠V T ⎢⎣⎝ ∂ 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
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
⎛ ∂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:
⎛ ∂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
(1) What is the maximum thermal efficiency that can be achieved by an engine
operating between these two reservoirs?
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.
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.
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
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.
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.
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
and S is constant.
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
Entropy
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 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
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.
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
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.
A+B=C+D
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)
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
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
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
1 ⎛∂U⎞ 1 ⎡⎛ ∂ U ⎞ ⎤
dS = ⎜⎜ ⎟⎟ dT + ⎢⎜⎜ ⎟⎟ + P ⎥ dV
So T ⎝ ∂ T ⎠V T ⎢⎣⎝ ∂ 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
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
⎛ ∂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:
⎛ ∂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
• Heat flows from higher to lower temperature. The flow is possible due to higher
thermal potential.
• Also higher electrical voltage is driving the electrons under the influence of
electrical potential as voltage.
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
• 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.
• 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
⎛∂U⎞ ⎛∂U⎞
dU = ⎜⎜ ⎟⎟ dS + ⎜⎜ ⎟⎟ dV
⎝ ∂ S ⎠V ⎝ ∂ V ⎠S
Thermodynamic Potentials
⎛∂U⎞ ⎛∂U⎞
• ⎜⎜ ⎟⎟ = T and ⎜⎜ ⎟⎟ = − P
⎝ ∂ S ⎠V ⎝ ∂ V ⎠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
⎛∂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
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 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.
(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
• 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.
∂G '
= S'.dT + V' dP + ∑ dn i
∂n i T , P , n1 ....
except n i
µ is an intensive variable
This gives a new sets of fundamental equations for the open systems.
⎛ ∂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
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
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
⎡ δΔG ⎤
⎢ δT ⎥ = −ΔS
⎣ ⎦P
on substitution
⎡ δ (ΔG )⎤
ΔG = ΔH − TΔS = ΔH + ⎢ ⎥
⎣ δT ⎦ P ,T
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
• 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.
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 )
• 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
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 )
Ttrans
c p(α )
• We have from the second law ∆SI =
∫
0 T
dT
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
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.