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An intoduction to basic Thermodynamics and the three laws

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Introduction

Thermo – Heat

Thermodynamics

Dynamics - Force

getting power from hot bodies or getting power from heat

Some are spontaneous processes that occur in nature and some are non-

spontaneous in nature but we cause them to occur

Introduction

higher elevation to lower elevation

Heat flows from high temperature to low temperature not the reverse

way but there are many processes which we cause to occur, they also do

not occur in the reverse way naturally

intermolecular energy is possible.

Introduction

• Thermodynamics is that branch of science which deals with the

study of the transfer and conversion of energy from one form into

other and its conversion to work.

• It deals with only conventional forms of energies like electrical,

mechanical, chemical. etc.

• The non-conventional energy like nuclear energy related to atomic

and sub-atomic particle forms has to be dealt separately because in

that case all matter would have to be considered as per the famous

Einstein s equation :

E = mC2 .

Introduction

metallurgical thermodynamics alone.

• The systems under discussions consisting of large no. of

particles i.e., macro systems.

Classification

Thermodynamics may be broadly classified into three :

• Classical: it treats a substance as continuum, ignoring behavior

of atoms and molecules. It consists of first, second and third

laws of thermodynamics

Introduction

theory, quantum theory and statistical mechanics allowed it to

arrive at macroscopic thermodynamic relations from atomistic

point of view.

deals with the application of thermodynamics to irreversible

processes such as chemical reactions.

thermodynamics

Introduction

Energy

It is the ability to do work. This is too mechanical an answer.

The broader definition is : it is the capacity to bring about changes in the

existing materials as per the requirements.

Forms of energies

• Mechanical: Kinetic, potential and configurational.

• Thermal: Heat exchanged.

• Electrical: Electrical energy = current x time x potential difference.

• Chemical: Chemical energy = no. of chemical bonds x bond strength

Introduction

studied

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

Introduction

subject of analysis.

Once the system is defined and relevant interactions with other systems

are identified.

Introduction

universe to which we will apply the laws of thermodynamics. We

call this subset a SYSTEM.

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

Motion).

which we focus our attention (eg: the water kettle or the aircraft

engine).

Introduction

system or thermodynamic system.

its chemistry during its study. If the system is undergoing

continuously some chemical change cannot be considered as system

• For example a live animate body like tree and human being are not

system. All inanimate aggregates are called systems as they have their

fixed chemistry

Introduction

Ø The rest of the universe outside the system close enough to the

system to have some perceptible effect on the system is called the

surroundings.

Important note: in engineering all equations must be dimensionally homogenous. This

means that every term in an equation must have the same units. It can be used as a sanity

check for your solution.

Example 1: Unit Conversion

The heat dissipation rate density of an electronic device is reported as 10.72 mW/mm2 by

Ø The surfaces which separates the system from the surroundings are

the manufacturer. Convert this to W/m2.

10720 (eg: walls of the kettle,

2

mW 1000mm 1W W

2

2

mm 1m 1000mW m

the housingClosed and Open Systems

of the engine).

A system is defined as a quantity of matter or a region in space chosen for study. The

mass or region outside the system is called the surroundings.

BOUNDARY

SURROUNDINGS

SYSTEM

Fig. 1: System, surroundings, and boundary

check for your solution.

Example 1: Unit Conversion

Introduction

The heat dissipation rate density of an electronic device is reported as 10.72 mW/mm2 by

the manufacturer. Convert this to W/m2.

2

mW 1000mm 1W W

10.72 10720

mm 2 1m 1000mW m2

Two types of exchange can occur between the system and its

Closed and Open Systems

surroundings:

A system is defined as a quantity of matter or a region in space chosen for study. The

mass or region outside the system is called the surroundings.

BOUNDARY

SURROUNDINGS

SYSTEM

Energy

Fig. 1: System, surroundings, and boundary

1. Energy

exchange (heat or work)

Boundary: the real or imaginary surface that separates the system from its surroundings.

2. Exchange of matter (movement of molecules across the boundary of

The boundaries of a system can be fixed or movable. Mathematically, the boundary has

zero thickness, no mass, and no volume.

theClosed system or control mass: consists of a fixed amount of mass, and no mass can cross

system and surroundings).

its boundary. But, energy in the form of heat or work, can cross the boundary, and the

volume of a closed system does not have to be fixed.

Open system or control volume: is a properly selected region in space. It usually encloses

a device that involves mass flow such as a compressor. Both mass and energy can cross

the boundary of a control volume.

Important note: some thermodynamics relations that are applicable to closed and open

systems are different. Thus, it is extremely important to recognize the type of system we

have before start analyzing it.

Introduction

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

systems

no mass is -permitted

in whichtono masstheis system

cross permitted to cros

boundary i.e. we would system

always boundary

consider i.e. we would

a system alwaysmass.

of constant consider a sy

do permit heat and ofwork

constant

: A closed or open system that does not exchange

We to mass.We

energy with

enter the

or dobut

leave permit

not heat and work to ent

mass.

eat.

leave but not mass.

Boundary Heat/work

Out

mass

system

CLOSED

SYSTEM Heat/work

m = const. in

energy

No mass entry or exit

Introduction

mass

Open system-

CLOSED in which weOpenpermitsystem-

mass toincross the system

which boundary

we permit mass in

to cross

either direction

SYSTEM (from the system to surroundings

boundary in either or vice(from

direction versa). Insystem to su

the

analysing open systems, weortypically

m = const.

vice lookInatanalysing

versa). a specifiedopen

region of space,

systems, we typic

energy

and observe what happens aatspecified

the boundaries

regionofofthat region.

space, and observe what hap

boundaries of that region.

Most of the engineering devices are open system.

osed system, mass cannot cross the boundaries, but energy can.

mass

Boundary

Heat/work Mass

Out out

CONTROL System

VOLUME

Heat/work

energy Mass in

In

ontrol volume, both mass and energy can cross the boundaries.

c The Internet is predominately used for consumer and business commerce.

Power generation

c Electricity plays a greater role throughout society.

Introduction

c Wind, solar, and other renewable technologies contribute a significant share of the nation's

electricity needs.

c A mix of conventional fossil-fueled and nuclear power plants provides a smaller, but still

significant, share of the nation's electricity needs.

c A smart and secure national power transmission grid is in place.

does not interact in any way with its surroundings is called

1.2.1 Systems

an isolated system

closed system A closed system is defined when a particular quantity of matter is under study. A

closed system always contains the same matter. There can be no transfer of mass

across its boundary. A special type of closed system that does not interact in any way

isolated system with its surroundings is called an isolated system.

When the valves are closed, we can consider

Figure 1.1 shows a gas in a piston–cylinder assembly. When the valves are closed,

the gas to be a closed system

we can consider the gas to be a closed system. The boundary lies just inside the pis-

ton and cylinder walls, as shown by the dashed lines on the figure. Since the portion

of the boundary between the gas and the piston moves with the piston, the system

Gas Boundary

volume varies. No mass would cross this or any other part of the boundary. If com-

bustion occurs, the composition of the system changes as the initial combustible mix-

ture becomes products of combustion.

1.2.2 Control

The Volumes

boundary lies just inside the piston and

cylinder walls

In subsequent sections of this book, we perform thermodynamic analyses of devices

such as turbines and pumps through which mass flows. These analyses can be con-

ducted in principle by studying a particular quantity of matter, a closed system, as it

passes through the device. In most cases it is simpler to think instead in terms of a

given region of space through which mass flows. With this approach, a region within

Fig. 1.1 Closed system: A gas a prescribed boundary is studied. The region is called a control volume. Mass crosses

Closed system: A gas in a piston–cylinder assembly.

in a piston–cylinder assembly. the boundary of a control volume.

A diagram of an engine is shown in Fig. 1.2a. The dashed line defines a control

control volume volume that surrounds the engine. Observe that air, fuel, and exhaust gases cross the

boundary. A schematic such as in Fig. 1.2b often suffices for engineering analysis.

Introduction

The system boundary should be delineated carefully before proceeding with any thermodynamic

Chapter 1 Getting Started

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articular animation

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standing.

and all of the piping. This boundary might be selected if the electrical power input

is known, and the objective of the analysis is to determine how long the compressor

The choice of a particular boundary defining a particular system depends heavily on the

must operate for the pressure in the tank to rise to a specified value. Since mass

convenience it allows in the subsequent analysis.

crosses the boundary, the system would be a control volume. A control volume

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A.1 – Tabs a, b, & c

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1.3 Describing particularly

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Engineers are interested in studying systems and how they interact with their sur-

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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.

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

Introduction

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, & c refers to (1) what is known about a possible system, particularly at its boundaries, and (2) the

animation A control volume enclosing only the compressor might be chosen if the condition of the air

objective of the analysis.

entering and exiting the compressor is known, and the objective is to determine the electric

tabs (Tabs a,

animation

for viewing

ce your

power input Figure 1.5 shows a sketch of an air compressor connected to a

storage tank. The system boundary shown on the figure encloses the compressor, tank,

. and all of the piping. This boundary might be selected if the electrical power input

is known, and the objective of the analysis is to determine how long the compressor

must operate for the pressure in the tank to rise to a specified value. Since mass

crosses the boundary, the system would be a control volume. A control volume

enclosing only the compressor might be chosen if the condition of the air entering

ystem_Types and exiting the compressor is known, and the objective is to determine the electric

– Tabs a, b, & c

power input. b b b b b

Engineers are interested in studying systems and how they interact with their sur-

Introduction

• At any given instant of observation the condition of the system is

described by an appropriate set of properties

• Limitations on the changes in these properties are set by the nature of

the boundary

• At the onset of the consideration of any problem classify the system

under study according to the following five categories

1. Closed vs open versus isolated

2. Unary vs multi-component

3. Homogeneous vs heterogeneous

4. Reacting vs non reacting

5. Otherwise simple vs complex

Introduction

species?

phases?

or mechanical effects involved? Are fields, surfaces, or elastic

effects involved?

Introduction

• Unary vs multi-component

Identifies the complexity of the chemistry of the system

Simplest chemical composition are unary à One chemical component

More than one chemical component à multi-component

• Homogeneous vs heterogeneous

Specific thermodynamic meaning à single phase

Mix of water and ice à composed of more than one phase

• Reacting vs non reacting

Systems that can exhibit chemical reactions.

• Otherwise simple vs complex

• Capable of energy exchange other than thermal, mechanical or chemical ch

i.e., gravitational, electrical, magnetic or surface influences then it is classi

complex category.

'surroundings'. The system may exchange matter or energy or both with the surroundings

during the change. The thermodynamic systens can be classified based on its interaction

Introduction

with the surroundings or on its orrun material distribution or on its o\,vn composition as shown

in Fig.1.1.

THEROMODYNAMIC SYSTEMS

INTERACT]ONS MATERIAL COMPOSITION

THE SURROUNDINGS DISTRIBUTION

gCHANG. MATTER AND CAN Q,A COMPONENT

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Introduction

We now introduce several terms and concepts used to describe systems

and how they behave.

Property

State

Process

To describe a system and predict its behavior requires knowledge of its

properties and how those properties are related.

volume, energy, pressure, and temperature to which a numerical value

can be assigned at a given time without knowledge of the previous

behavior (history) of the system.

Introduction

State

properties

Since there are normally relations among the properties of a system, the

state often can be specified by providing the values of a subset of the

properties

focus (SYSTEM)

T, P, XK, V

Boundary

State

• Condition of the system as described by its properties.

• Usually only a subset of properties need to be specified

to identify the state of a system.

• Some difficulties in specifying “state” of a system.

– State of the world

– State of the “hot potato”

Introduction

some prefixed axes, similarly the state of a system is described by some

experimentally determinable parameter which can lead to the complete

reproduction of the system.

• The minimum number of variable required to describe the state of the system

are called independent state variables.

Introduction

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

• All other variables whose values get fixed with the specification of

independent state variables are referred to as dependent state variables.

Introduction

Intensive Extensive

of the system it is known as extensive state property. For example: Mass,

Volume, weight, length, energy etc.

intensive state property. For example: temperature, pressure, conductivity,

density, colour, odor, malleabilty, hardness, specific heat, molar volume etc.

Intensive and Extensive Properties

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

Introduction

properties which are independent of the size or extent of the system. The properties like volume,

which depend on the size of the system are called extensive properties. The properties, like

temperature and pressure which are independent of the mass of the system are called intensive

properties. The test for an intensive property is to observe how it is affected when a given system is

combined with some fraction of exact replica of itself to create a new system differing only by size.

Assume two identical systems S and S as shown in Figure . Both the

Intensive properties are those which are unchanged by this process, whereas those properties

whose values are increased or decreased 1 in proportion to2 the enlargement or reduction of the

systems are in identical states.

system are called extensive properties.

Assume two identical systems S and S as shown in Figure 2.1 . Both the systems are in identical

1 2

Let S3 be the combined system.

states.

Let S be the combined system. Is the value of property for S same as that for S (and S )?

3 3 1 2

Figure 2.1

Is the value Ifof property for S3 issame

the answer is yes, then the property intensive

as that for S1 (and S2 )?

If the answer is no, then the property is extensive

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

Ifspecific

theinternal

answer is no, then the property is extensive

energy, u = U/m

Similarly, the molar properties are defined as the ratios of the properties to the mole number (N) of

the substance

Introduction

• Comparison of two systems :

Both have identical intensive properties

Double the quantity of matter à double the extensive properties

Many thermodynamic analysis consists mainly of carefully accounting for

changes in extensive properties as system interacts with surroundings.

Are not additive in the sense previously considered

Values independent of the size of the system and many vary from place to

place within the system at any moment

• Extensive properties àfunction of time

Intensive properties: are those that are independent of the size (mass) of a system, such

Introduction

as temperature, pressure, and density. They are not additive.

Extensive properties: values that are dependant on size of the system such as mass,

volume, and total energy U. They are additive.

Example:- Temperature, pressure, density, boiling point,etc

canGenerally, uppercase letters are used to denote extensive properties (except mass

have a different value at different points

m), and lower case letters are used for intensive properties (except pressure P,

temperature T).

Pressure varies

Extensive withper height

properties as well

unit mass as horizontally.

are called specific properties, e.g. specific

volume (v=V/m).

extensive

m properties 0.5m 0.5m

V 0.5V 0.5V

T

P T T

P P

intensive

properties

Fig. 1‐5: Intensive and extensive properties of a system.

Introduction

• Example:- Temperature, pressure, density, boiling point

Pressure varies with height as well as horizontally.

properties defined in thermodynamics

properties in a small region of the system

ratio of small volume element neighbouring the point (∆V) and the

number of moles of component (∆nK )

Introduction

Extensive properties are not just dependent on the amount of material

in a system

Total mass à 2 g

Squaring total mass à 4g2

Squaring and summing individual masses à 2g2

Introduction

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

Introduction

extensive state variable.

For example: Density = m / V

properties, which are intensive and become independent of

quantity of matter and hence of more general applicability.

Introduction

At a given state, each property has a definite value that can be assigned

without knowledge of how the system arrived at that state.

state to another is determined, therefore, solely by the two end states

and is independent of the particular way the change of state occurred

Thermodynamics also deals with quantities that are not properties, such

as mass flow rates and energy transfers by work and heat.

Introduction

externally or internally imposed constraints, in

terms of their state variables from the existing one

to some different values.

may be called as a thermodynamic process.

Introduction

Process

When any of the properties of a system changes, the state changes and

the system is said to undergo a process

Process System

System

T, P, X, V

Introduction

Many a times such processes are carried out under additionally imposed conditions and are

named accordingly. Such processes are:

without any change in temperature of the system e. g. melting of

ice or metal. dT = 0

any change in pressure of the system e.g. processes carried out in

open atmosphere. dP = 0

without any change in volume of the system e.g. the processes

carried out in vessel of known volume . dV = 0

ryray

or it

Introduction

nray not be known.

There can be sereral such relationships correlating the available state propedies

of a particular system and all such relationships shali be called as equations of state for

that particular system. These are useful relationships to calculate the required

state

properties' knowing sone others.

• Adiabatic processes: These are the processes which proceed

1.7 THEREMODYNAMIC PROCESS

A material undergo a change,

system may externally under or internally irnposed

in to sorne different

a change in the state of the system is known as

surrounding e.it g. two

the system into is pieces

pieces. But if the

into

completely

lf a ten meter long rod is cut

of

in

two

process

insulated

the energy

breaking, to

of

from the

the change is merely a physical one

the rod

required break

breaking

is

of breakingγ to be a thernnodynamic

surrounding . dq = similarly

0. for if ironideal gas PVto form=itsconst.

oxide, it is aγ = Cp/Cv

taken into the

consideration then process is considered

withcombines oxygen simple chemical

process.

process but if the energy exchanged in this process is taken into account

then this process

process takes place

• Polytropic Processes: Those processes which obey equation

of oxidation is a thermodynamic process' The way the thernndynamic

is known as its

,process path'. There are different types of thermodynamic processes

named accordingly and are

depending upon the conditions imposed on the system and are

PVn = const where n is any positive number between 1 and γ.

shown in Fig. 1.2.

lsoBARlc

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Sc he matic tion of

re Pre s e nta

tr G

E ous

f o tkermodYnamic Proc-

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rt (, €.ss'es like isabaric,

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o. kolhermal, isochoric, adi-

abatic and polytroPic-

VOLIJME

Introduction

If a system exhibits the same values of its properties at two different

times, it is in the same state at these times

with time.

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.

assessed

time without knowledge Theof the pastofhistory

value aand of the

property of system.

a systemMany other properties

is independent of the are considered

during the course

volume, of

energy, our study.

pressure temperature to which numerical values canprocess or theatpaa

be assigned

during the course of our study.

system in reaching a particular state.

time without knowledge of the past history of the system. Many other properties are cons

Theofvalue

The value Introduction

during the course of our study.

of a

a property

The property

of a system

change ofisvalue

in the aindependent

system

of theisproperty

independent

of the process

dependsofonly

or thepath

the process

on followed

the or and

initial thethe

by path

the f

system system in

in reaching reaching

a particulara particular

state. state.

The value of a property of a system is independent of the process or the path followed

Thesystem

word in reaching

state refers a particular state.

to the condition of a system as described by its proper

The change in the value of the property depends only on the initial andonthethefinal states.

Mathematically, if P is a property of the system, then the change in the

The change in the value of the property depends

The change in ifthe

only initial and the fin

Mathematically, P value of the property

is a property of thedepends

system,only

thenon the

the initial

change andinthe final

the states.

property

property in going from the initial state 1 to the final state 2 is given by

The word state refers

The wordinitial

to the1condition

statestate

referstoto finalof

thethe a system

state

condition

as described

2 is given by

of a system

by its properties.

as described by its propertie

The word state refers to the condition of a system as described by its properties.

Mathematically, if P is a property of the system, then the change in the property in going from the

Mathematically,

initial state if P 2ifisis

1 toMathematically,

the final state Pagiven

isproperty

a property

by ofof the system,then

the system, then

the the change

change in the in the property

property in going frin

initial state

initial1state

to the

1 tofinal state

the final 2 2isisgiven

state by

given by

• If a system has two independent variables say x and y and any other

If P = P (x, y) then,

function or property can be expressed in its total differential form

If P = P (x, y) then,

If P = P (x, y) then,

P

If P = P (x, y) then, = P (x, y)

where,

where, where,

where,

If,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

and temperature, T, of the gas

V =V(P,T)

Fixing the values of any two of the three variables fixes the value of

the third variable of the system when it is in equilibrium

b P2

T

T1 T2 Introduction

P P1

In a three-dimensionalP2diagram, the coordinates of which are volume,

pressure,

quilibrium and

states of temperature,

existence theofpoints

for 1 mole gas inin V-P-T

V -P space

-T space, which

shown represent the

to lie

T1 T2

urface.equilibrium

P states of existence

6 of the system lieTOon

INTRODUCTION THEaTHERMODYNAMICS

surface OF MATERIALS,

V

quilibrium states of

Consider ∆V = Vwhich

a existence

process − 1V1mole

2for of gasthe

changes in Vstate

-P -T space,

of shown to lie

urface.

the gas from state 1 to state 2

ld proceed along many different paths on the V -P -T surface, two

→ 2 and 1 → b → 2, are shown in Figure 1.1. Consider the path a

∆V = V2 − V1 1

change in volume is

2

ld proceed along many different paths on the V -P -T surface, two

b

2,Vare

1 →a shown 2 Figure 1.1. Consider the path

change in volume is P1

∆V = (Va − V1 ) + (V2 − Va ) P2

∆V = ∆V1 →a + ∆Va →2 P

T1 T2

∆V = V2 − V1

∆V = (Va − V1 ) + (V2 − Figure

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

on a surface.

at the constant temperature, T2 ∆V = V2 − V1

at the constant pressure, P1 Introduction

satthese

the constant

changestemperature,

where: as T2

1 → a occurs at the constant pressure, P1

→ 2 occurs

ss thesea changes as at the constant

T2 temperature, T2

⎛ ∂V6 ⎞

∆V1→a = V a − V1 = ⎜

T 2⎝ ∂

We can express these TchangesT∫ ⎟

⎠ as

dT

INTRODUCTION TO THE THERMODYNAMICS OF MATERIALS,

⎛ ∂V ⎞P1

∫

1

V

∆V1→a = V a − V1 = ⎜ ⎟ dT

⎝ ∂ T ⎠ T2

T

⎛ ∂V ⎞

∫

1 P1

∆V1→a = V a − V1 = ⎜ ∂T ⎟ dT

P2 ⎝ ⎠

⎛ ∂V ⎞

∫

T1 P1 1 a

∆V a→2 =OF

ON AND DEFINITION

−Va = ⎜

V 2TERMS ⎟ dP 7

P⎝ ∂ P ⎠

and P1 2

2

⎛ ∂V ⎞T 2 b

∆V a→2 = V 2 − V a = ⎜

⎝ ∫

∂P ⎠ ⎟ dP

P2

⎛ ∂V ⎞

T

∫

P1 P1

T2

T2 ∆V

P2 a → 2 = V 2 − V a = ⎜ ∂P ⎟ dP P2

⎛ ∂V ⎞ ⎛ ∂V ⎞ ⎝ ⎠ T

∆V =

1→2

∫ ⎜⎝ ∂T ⎟⎠

T1

dT +

P1

∫ ⎜⎝ ∂P ⎟⎠

P1

dP P

T2

T

P

1 1 T2 (1.2)

2

on a surface.

⎛ ∂V ⎞ ⎛ ∂V ⎞ ⎛ ∂V ⎞ ⎛ ∂V ⎞

e path 1 → b∆V→1→2:

∆V 1→2 =

T2 ⎝ ∫

⎜ ∂T ⎟

⎠

⎛T1∂V ⎞ P1

dT ∆V

+

P 2

⎜1→

⎝ ∂P ∫

2 ⎟=

⎠

P⎛1 ∂V ⎞ T 2 ⎝

dP

⎜ ∂T ∫ ⎠ ⎝ ∫

⎟ dT + ⎜ ∂(1.2)

P⎠⎟ dP

2 = ⎜ ∂T ⎟ dTIntroduction

∫ + ⎜

∫ ⎟ dP

T1 P1 P 1 (1.2) T2

T1

⎝ ⎠ P

⎝ ∂P ⎠

P1 T2

y, for the path 1 → b → 2:

1

P2

∂V→⎞ b → 2:

⎛1

Similarly, for the path

∆V 1→b = V b − V 1 = ⎜

or the path 1 → b → 2: ⎟ dP

⎝ ∫

∂P2P⎛ ∂⎠V ⎞

P2 ⎝ ∂P ⎠ ∫

∆V 1→b = V b − VP11 = ⎜ 6 T1 ⎟ dPINTRODUCTION TO THE P 2

THERMODYNAMICS OF MATERIALS,

⎛ ∂V ⎞

∫

⎛1 ∂V ⎞ T1

∫

P

∆V 1→b = V b − V 1 = ⎜ ∆V

⎟ 1→b = V b − V 1 =

dP ⎜

V ⎟ dP

P

⎝ ∂P ⎠

1 T1

⎝ ∂P ⎠ P1 T1

T2

⎛ ∂T 2V ⎞

and

∆V b→2 = V 2 − V b = ⎜

∫ ∫

⎛ ⎟

∂V

dT

⎞

∆V b→2 = V 2 − VTb ⎝= ∂P⎜ ⎠ ⎟ dT a

⎝ ∂P ⎠

1 T2 P2 1

⎛ ∂V ⎞

∫ ⎜⎝ ∂P ⎟⎠

T1 P2

∆V b→2 = V 2 − V b = dT T2 2

⎛ ∂V ⎞

∫

b

P2

T1

T2

∆V b→2 = V 2 − V b =

P2

⎜ ∂P ⎟ dT T

⎛ ∂V ⎛⎞ ∂V ⎞ ⎛ T∂2V⎛ ∂⎞V ⎞ ⎝ ⎠

∫ ∫ ∫ ∫

P2

∆V 1→2∆V

= ⎜ = ⎟ dP +dP +⎜ ⎟ dTdT T1 P 2 P1

(1.3)

1→2 ∂P ⎜

⎝ P2 ⎝⎠ ∂P ⎟⎠ T⎝2 ∂T

⎜ ∂⎠T ⎟ (1.3) P2

⎝ ⎠

P1

⎛ ∂V ⎞ ⎛ ∂V ⎞ T1

∫ ∫

P1 T1 T1 P2 P2

Hence,

∆V 1→2 = ⎜ ⎟ dP + ⎜

T1

⎟ dT T1 T2

(1.3)

⎝ ∂P ⎠ ⎝ ∂T ⎠ P

P1 T1 T1 P 2 P2 T2

nd 1.3 must yield the same value of

s 1.2 and 1.3 must yield the same value ∆ V 21→.⎛2In

of ∆ V

Figure 1.11→The

.∂Vthe

In ⎞ limit

the limit of ⎛infini-

of infini-

∂V ⎞for 1 mole of gas in V-P-T sp

change in volume,

in volume, thesethese equations

equations ∆V

yieldyield = complete

2 the

the

1→

equilibrium

⎜a surface.

oncomplete dP + ⎜ of

states of existence

⎟ differential

differential of⎟ dT

P2 ∆VT = V2 − V1

2

⎛ ∂V ⎞ ⎛ ∂V ⎞

∫ ∆V 1→2

∫ = ⎜

P1

⎝

⎟

∂P ⎠

dP + ⎜

Introduction

T1 T

⎝

⎟

∂T ⎠

process could proceed along many different paths on the

1

dT

(1

P2

uations 1.2 and 1.3 must yield the same value of ∆ V 1→ 2 . In the limit of infi

→ In

aimal 2. The

the change

limit of in volume

infinitesimal change

change in volume, these equations

is

in volume,

yieldthese

the equations

completeyield the

differential

uationcomplete

1.1: differential

⎛ ∂V ∆

⎞V = ∆ ⎞ a + ∆Va →2

⎛ ∂VV1 →

dV = ⎜ ⎟ dP + ⎜ ⎟ dT (1

⎝ ∂P ⎠T ⎝ ∂T ⎠ P

∆V = (Va − V1 ) + (V2 − Va )

e change in volume caused by changing the state of the gas from state 1 to stat

pends The

onlychange

on the in volumeatcaused

volumes statesby changing

1 and 2 andthe state of the gas

is independent of from statetaken

the path

1 to statethe

gas between 2 depends only on

states. This is because ∆V

the volumes =states

the at V2 −1ofV

volume and

the2 and is

1 gas is a state functi

independent of the path taken by the gas between the states. This is

d Equation 1.4 is an exact differential of the volume, which is a thermodynam

because the volume of the gas is a state function

te variable.

e:The partial differentials which relate the change in volume to changes in t

→ a occurs

ensive at the constant

thermodynamic variables (Ppressure,

and T ) are Prelated

1 to the properties of t

→— namely,

2 occurs at the constant temperature, T

Relationship among state variables

Let there be three state functions X, Y and Z and two of these as

independent state variables. Once Z and once Y as dependent

variables. Thus

Z = Z (X, Y)

Y = Y (X, Z)

Total differential can be written as

⎛ ∂Z⎞ ⎛ ∂Z⎞

dZ = ⎜⎜ ⎟⎟ dX + ⎜⎜ ⎟⎟ dY

And ⎝ ∂ X ⎠Y ⎝ ∂ Y ⎠X

⎛∂Y⎞ ⎛∂Y⎞

dY = ⎜⎜ ⎟⎟ dX + ⎜⎜ ⎟⎟ dZ

⎝ ∂ X ⎠Z ⎝ ∂ Z ⎠X

Relationship among

state variables

Putting the value of dY in first expression leads to

⎡⎛ ∂ Z ⎞ ⎛ ∂Z ⎞ ⎛∂Y⎞ ⎤ ⎡ ⎛ ∂Z ⎞ ⎛∂Y⎞ ⎤

dZ = ⎢⎜⎜ ⎟⎟ + ⎜⎜ ⎟⎟ ⎜⎜ ⎟⎟ ⎥ dX + ⎢ ⎜⎜ ⎟⎟ ⎜⎜ ⎟⎟ dZ ⎥

⎢⎣⎝ ∂ X ⎠ Y ⎝ ∂ Y ⎠ X ⎝ ∂ X ⎠ Z ⎥⎦ ⎢⎣ ⎝ ∂ Y ⎠ X ⎝ ∂ Z ⎠ X ⎥⎦

Sides, we get

⎛ ∂Z ⎞ ⎛∂Y⎞ ⎛ ∂Z⎞ 1

⎜⎜ ⎟⎟ ⎜⎜ ⎟⎟ = 1 ⇒ ⎜⎜ ⎟⎟ =

⎝ ∂ Y ⎠X ⎝ ∂ Z ⎠X ⎝ ∂ Y ⎠ X ⎛⎜ ∂ Y ⎞⎟

⎜ ∂Z⎟

⎝ ⎠X

⎛ ∂Z⎞ ⎛ ∂Z ⎞ ⎛∂Y⎞ ⎛ ∂Z⎞ ⎛ ∂Z ⎞ ⎛∂Y⎞

and ⎜

⎜ ⎟

⎟ ⎜

+⎜ ⎟

⎟ ⎜

⎜ ⎟

⎟ =0 ⇒ ⎜

⎜ ⎟

⎟ = − ⎜⎜ ⎟⎟ ⎜⎜ ⎟⎟

⎝ ∂ X ⎠Y ⎝ ∂ Y ⎠X ⎝ ∂ X ⎠Z ⎝ ∂ X ⎠Y ⎝ ∂ Y ⎠X ⎝ ∂ X ⎠Z

Relationship among

state variables

Similarly, ⎛∂Y⎞ 1 ⎛ ∂Z⎞ 1

⎜⎜ ⎟⎟ = ⎜⎜ ⎟⎟ =

⎝ ∂ X ⎠ Z ⎛⎜ ∂ X ⎞⎟ and ⎝ ∂ X ⎠ Y ⎛⎜ ∂ X ⎞⎟

⎜∂Y⎟ ⎜ ∂Z⎟

⎝ ⎠Z ⎝ ⎠Y

Finally after substitution we can write

⎛ ∂Z⎞ ⎛∂Y⎞ ⎛∂X⎞

⎜⎜ ⎟⎟ ⎜⎜ ⎟⎟ ⎜⎜ ⎟⎟ = − 1

⎝ ∂ Y ⎠X ⎝ ∂ X ⎠Z ⎝ ∂ Z ⎠Y

similarly

⎛∂X⎞ ⎛∂Y⎞ ⎛ ∂Z ⎞

⎜⎜ ⎟⎟ ⎜⎜ ⎟⎟ ⎜⎜ ⎟⎟ = − 1

⎝ ∂ Y ⎠Z ⎝ ∂ Z ⎠X ⎝ ∂ X ⎠Y

The above two expressions correlate the partial differentials of three state

variables w.r.t one another and are popularly called reciprocity theorem.

Introduction

be useless. Discuss this assertion.

then the behavior of all aspects of matter would depend

explicitly on the history of the system.

There would be no variables that, by themselves,

explicitly describe the current condition of any system.

Even the history experienced by the system could not be

described in terms of some sequence of its properties.

MM209 - Thermodynamics

Instructor : Aswani Yella

Introduction

• System, boundary, surroundings

• Different thermodynamic systems

• Property, state, process

• Intensive and extensive variables

• State Postulate

• State and process functions

differential

⎛ ∂a ⎞ ⎛ ∂b ⎞ ⎛ ∂ X ⎞ ⎛ ∂Y ⎞ ⎛ ∂ Z ⎞

⎜ ⎟ =⎜ ⎟ ⎜ ⎟ ⎜ ⎟ ⎜ ⎟ = −1

⎝ ∂y ⎠ X ⎝ ∂x ⎠Y ⎝ ∂Y ⎠Z ⎝ ∂ Z ⎠ X ⎝ ∂ X ⎠Y

Introduction

be useless. Discuss this assertion.

then the behavior of all aspects of matter would depend

explicitly on the history of the system.

There would be no variables that, by themselves,

explicitly describe the current condition of any system.

Even the history experienced by the system could not be

described in terms of some sequence of its properties.

Introduction

Driving forces and their conjugates:

All thermodynamic potentials are expressed in terms of conjugate pairs.

Many of the direct observables form conjugate pairs such that their

product has the dimensions of energy or sometimes power.

force times small displacement.

Similar situation exists in thermodynamics.

expressed as the sum of the products of certain “Generalized forces” that

when unbalanced causes certain “Generalized displacements”.

Introduction

variables.

Displacement à extensive variable

Yielding an extensive energy transfer

Introduction

variables.

System Intensive variable Extensive

variable

Fluid Pressure P Volume V

Filament Tensional force F Length L

Film Surface Tension r Area A

Electrical Potential difference E Charge q

Dielectric Electric field E Dipole moment P

Magnetic Flux density B Dipole moment m

All system Temperature T Entropy S

Generalized Force F Displacement x

Introduction

Thermodynamic Equilibrium

• When a system is placed in a new set of surroundings, it

usually be seen to undergo a change.

• Bulb of thermometer -- beaker of warm water

• Mercury expands and will rise in the capillary, after

sometime there is no further change (thermodynamic

Equilibrium)

Introduction

In mechanics, equilibrium means a condition of balance maintained by an equality of

opposing forces.

In thermodynamics, the concept is more far-reaching, including not only a balance of forces

but also a balance of other influences.

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

position

Neutral Equilibrium

If ball is moved from its position it will roll off the hill, until it

finds a stable point

Unstable Equilibrium

back. But, moderated displacement will cause the ball to roll

down the other side of the hill Metastable Equilibrium

Introduction

Unstable Equilibrium

neither mechanics nor thermo knows, truly unstable equilibrium, equilibrium defined on

microscopic variables, large scale averages of quantities which on microscopic scale are subject to

fluctuations

Eg: Pressure exerted by a gas (macroscopic average of impulses from discrete molecular impacts)

Introduction

H2O vapors

H2O vapors H2 + O2

H2O liquid

to their initial states if Stable to small displacements

constant T Large compression leads to

displaced/released Vapor pressure depends raise in T that it could explode

on T

Introduction

infinetesimal change in one or more of the state variables

is said to be a reversible process.

• A classical example of this is the gas cylinder and piston.

If the pressure of the gas is say P atm and (p+dp) is

exerted from outside on the piston, the gas inside the

piston shall be compressed. However, if the external

pressure is (p-dp) then the gas shall expand.

Introduction

process can not be reversed by changing one or

other parameters. Once burnt can not be

reproduced by reversing the process. This is

typically a Irreversible process.

• Other examples are mixing of two gases, mixing

of two liquids to form a solution or flow of

electric current through resistor.

• All natural processes are irreversible.

Introduction

Thermodynamic reversibility

Process must not have “Hysteresis”

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

equilibrium state

system

piston, then sound waves or shock waves are setup in the gas and

change is not reversible

Introduction

retrace its previous path but proceeds by a different one

Thermodynamic equilibrium (TE)

• A system is in (a) thermodynamic equilibrium (state) if it

undergoes no changes when isolated from its surroundings.

• Given unchanging surroundings, the system will remain

unchanging if it is in equilibrium.

• Equilibrium correspond to a state of balance; the system is “at

peace” with all its parts and with its surroundings.

• Intuitively, non-equilibrium is identified from the existence of

“currents” or “flows” or “fluxes” such as heat flow, chemical

diffusion, electric currents etc. arising from certain “driving

forces” corresponding to the “imbalances” discussed above.

Thermodynamics studies the passage of system from one equilibrium state to another

equilibrium state. Often the passage itself is idealized using the concept of thermodynamic

Equilibrium (see later).

Introduction

gradient in the system.

• Thermal Equilibrium: if there is no temperature

gradient in the system.

• Chemical Equilibrium: if the rate of forward reaction

is equal to rate of backward reaction.

• Complete thermodynamic equilibrium is thus that

situation where the system is in equilibrium with

respect to all such potentials like mechanical, thermal

and chemical.

Thermal equilibrium & Zeroth Law

independent variables for describing the state of the system

X- Generalised force

Y- Generalised displacement

system to remain constant

systems

Thermal Equilibrium – two different boundaries

Thermal equilibrium & Zeroth Law

Adiabatic Boundary

Diathermic Boundary

equilibrium state for system values of X, Y, X’, Y’

A may coexist with any Will change spontaneously

equilibrium state of B for until an equilibrium state of

all attainable values of the the combined system is

quantities X, Y, X’, Y’ reached

Thermal equilibrium & Zeroth Law

• When a “hot” body is placed in contact with a “cold” body through a part

of their boundary that allows passage of heat, the properties of the body

change initially due to heat transfer between them. Eventually the heat

transfer stops and the properties no longer change with time. The two

bodies have reached thermal equilibrium.

The two systems are said to be in thermal equilibrium with one another

Thermal equilibrium & Zeroth Law

The two systems are said to be in thermal equilibrium with one another

characterized by restricted values of the coordinates of the systems,

after they have been in communication with each other through a

diathermic wall

Thermal equilibrium & Zeroth Law

Now imagine two systems A and B separated from each other by

adiabatic wall but each in contact simultaneously with a third system C

through diathermic walls and the whole system surrounded by adiabatic

walls

Thermal equilibrium & Zeroth Law

If, of three systems A, B and C:

• system A is in thermal equilibrium with system C,

• system B is in thermal equilibrium with system C,

Then:

systems A and B are in thermal equilibrium with each other.

thermal equilibrium with each other

when interaction is allowed between the systems through a

shared diathermal no-work boundary”

Thermal equilibrium & Zeroth Law

Temperature is a measure of hotness of a given macroscopic object,

as felt by a human body

equilibrium established in zeroth law of thermodynamics

another system B in state X1’, Y1’

second state X2, Y2 that is in thermal equilibrium with the

original state of system B X1’, Y1’

Thermal equilibrium & Zeroth Law

All such states when plotted on XY diagram lie on a curve

system is in thermal equilibrium with one state of another system

Thermal equilibrium & Zeroth Law

that they are in thermal equilibrium with one another

ensures them being in thermal equilibrium with one another

a system is in thermal equilibrium with other systems

Zeroth Law : Implications

in figure and have an easily measurable

property such as “mercury level” which

changes only in response to energy

interactions through diathermal no-work

walls.

“two systems A and B must be in thermal equilibrium if they have

resulted in the same mercury level on thermal contact with a standard

body C of the type shown in the figure”

Zeroth Law : Implications

• “mercury level, as recorded by C” is a variable

characterizing thermal equilibrium just in the

same way pressure of a simple compressible

C system is a variable of “mechanical

equilibrium”.

states of A/B, C may be made “small enough”

in size compared to A/B. Then the mercury level

variable can be given the fancy name

temperature and considered the property of A/B

responsible for thermal equilibrium.

as a new property from the third law and concept of thermal

equilibrium, when both are expressed mathematically.

Specific Volume, Pressure & Temperature

If we want to know if two objects are at the same temperature, it is not necessary to bring them

into contact and see whether their observable properties change with time.

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

third object is usually a thermometer.

Any object with at least one measurable property that changes as its temperature changes can be

used as a thermometer. Such a property is called a thermometric property

The particular substance that exhibits changes in the thermometric property is known as a

thermometric substance.

Specific Volume, Pressure & Temperature

20 Chapter 1 Getting Started

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.

tor types are called thermistors. A battery-powered electrical-resistance thermometer

As temperature increases, the liquid expands in volume and rises in the capillary. The length L

commonly used today is shown in Fig. 1.13b.

of the liquid in the capillary depends on the temperature

A variety of instruments measure temperature by sensing radiation, such as the

ear thermometer shown in Fig. 1.13c. They are known by terms such as radiation

thermometers and optical pyrometers. This type of thermometer differs from those

previously considered because it is not required to come in contact with an object to

determine its temperature, an advantage when dealing with moving objects or objects

Electrical resistance sensors are based on the fact that the electrical resistance of various

at extremely high temperatures.

materials changes in a predictable manner with temperature.

ENERGY & ENVIRONMENT The mercury-in-glass thermometer once

prevalent in home medicine cabinets and industrial settings is fast disappear-

ing because of toxicity of mercury and its harmful effects on humans. The

A variety of instruments measure temperature by sensing radiation, such as the ear

American Academy of Pediatrics has designated mercury as too toxic to be pres-

ent in the home. After 110 years of calibration service for mercury thermometers,

thermometer. They are known by terms such as radiation thermometers and optical pyrometers.

the National Institute of Standards and Technology (NIST) terminated this service in 2011 to

encourage industry to seek safer temperature measurement options. Alternative options for

home and industrial use include digital electronic thermometers, alcohol-in-glass thermom-

Temperature Scales

The tendency of the liquid in a glass thermometer to freeze at low temperatures imposes a

lower limit on the range of temperatures that can be measured. At high temperatures liquids

vaporize and therefore these temperatures also cannot be determined using glass thermometers

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

Thermal equilibrium & Zeroth Law

• To establish an empirical temperature scale, we select

some system with X-Y coordinates as a standard , and

adopt a set of rules assigning numerical value to

temperature associated

Choose any convenient path in the X-Y plane,

which intersects the isotherms at the same Y

coordinate but a different X Coordinate

taken to be a convenient function of the X at the

intersection point

thermometric function t(x) determines the empirical temperature scale

Thermal equilibrium & Zeroth Law

property

Thermal equilibrium & Zeroth Law

Let us decide arbitrarily that the empirical temperature θ is directly

proportional to X to define the temperature scale

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

arbitrarily chosen standard state in a reproducible state

point, that is a fixed temperature

temperature scales

Thermal equilibrium & Zeroth Law

Before 1954, the international metric was based on the temperature

interval between two fixed points : Celsius scale

2. Steam point

as the basis for a new international

temperature scale : Kelvin scale

Thermal equilibrium & Zeroth Law

Thermal equilibrium & Zeroth Law

Thermal equilibrium & Zeroth Law

For a Thermocouple

Thermal equilibrium & Zeroth Law

No thermometer compared in effectiveness with gas thermometer

the temperature of a gas at constant volume increases

monotonically with pressure

the system whose temperature is to be measured. The mercury column is so

el of mercury stands at the reference mark S . This ensures that the volume of

Thermal equilibrium & Zeroth Law

a constant value. Let the pressure of the gas be read as P. Let a similar

de when the gas bulb is maintained at the triple point of water, Ptp. We can

putting water and ice in an insulated chamber and evacuating air ( which is then

Objectives_template 10/04

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

5.5.

Figure 5.5

Figure 5.4 When these curves are extrapolated to zero pressure, all of them yield the same intercept. This

behaviour can be expected since all gases behave like ideal gas when their pressure approaches

zero. The correct temperature of the system can be obtained only when the gas behaves like an

ideal gas, and hence the value is to be calculated in limit Ptp 0. Therefore

he triple point of water has been assigned a value of 273.16 K. Since for an

P, , as

Rankine & Fahrenheit Temperature Scales

The Rankine scale, the unit of which is the degree rankine ( R), is

proportional to the Kelvin temperature according to

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

Kelvin or Rankine scale unless specifically stated otherwise.

Temperature Scales

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

as the kelvin

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

temperature scales.

MM209 - Thermodynamics

Instructor : Aswani Yella

Work

If a system undergoes displacement under the action of force, work is said to be done

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

If a system as a whole exerts force on its surroundings and a displacement takes place, the work

that is done either by the system or on the system is called external work

Eg: Gas confined in a cylinder and at a uniform pressure, while expanding and imparting motion

to a piston does external work on its surroundings

The work done however by one part of a system on another part is called internal work

Eg: Interactions of molecules, atoms or electrons on one another constitute internal work

Work

Internal work Not dealt in Macroscopic thermodynamics

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

Hydrostatic system: Closed cylinder equipped with a frictionless movable piston on which the

system and the surroundings may act.

Pressure exerted by the system at the piston face is P

Force on the internal surface of the piston = PA

Now if apply an external force on the piston that the piston moves in an infinitesimal distance dx

during compression, then the surroundings perform an infinitesimal amount of work dW

dW=Fdx= PAdx

Work

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

Work

As the volume of hydrostatic system changes because of the motion of a piston in a cylinder, the

position of the piston at any moment is proportional to volume

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

Pressure and the volume changes of a gas during expansion can be indicated as a curve on PV

diagram

Work

The integral for this process is evidently the shaded area under curve I which represents the work

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

According to the sign convention for work, work is done by the system in curve I and work is

done on the system in curve II

Work

Hydrostatic work depends on the path

I to b to f work done is equal to –PoVo

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

only depends on the initial and

final states but also on the path

of integration

for a quasi-static process the

expression cannot be

integrated until P is specified

as a function of V using

appropriate equation of state

Work

Energy

Energy is often defined as the capacity to produce work

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

The 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

Energy (PE) in its kinetic energy.

A Figure mass m is moved from an initial elevant Z1 to a final elevation Z2(Fig

body of 3.1

3.1)

The force on the body, F = mg

This force has moved a distance ( Z2 - Z1) . Therefore, the work done on the

A body of mass m is moved from an initial elevant Z1 to a final elevation Z2

body

The kinetic energy and potential energy are also called organized form of energy that can be

readily converted into work.

The kinetic energy and potential energy are also called organized form of energy that can be readily

converted into work.

Module 1 :

Lecture 3 : Energy and Processes

Energy

Microscopic modes of

Microscopic energy of energy

modes

TheThe

microscopic modesmodes

microscopic of energy

of refer to the

energy energy

refer stored

to the in the stored

energy molecular and molecular

in the atomic and ato

structure of the system.

the system.

The molecules are in random motion. A molecule possesses energy in several forms.

The molecules are in random motion. A molecule possesses energy in several forms

• Translational energy, Rotational energy, Vibrational energy

• Electronic energy, Chemical

Translational energy,

energy, Nuclear energy

Rotational energy, Vibrational energy.

Electronic energy, Chemical energy, Nuclear energy.

If ε Ifrepresents energyenergy

ε represents of one molecule, then

of one molecule, then

N major

is thetasks

totalinvolved

number in of molecules inis the

thermodynamics system,

devising meansthen the total amount of micr

for converting

energyenergy into useful or organized work

disorganized

U=Nε

Relationship between work & heat

There are other means of changing the state of the system that do not necessarily involve the

performance of work

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

temperature to slightly higher temperature

Relationship between work & heat

Consider four different processes which involve closed systems

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

falling weight

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

Relationship between work & heat

Consider four different processes which involve closed systems

in contact with the burning gases at a high temperature

the system is near by but not in contact with a lamp whose

temperature is higher than that of water

the agency of change cannot be described by mechanical means

Relationship between work & heat

Upto the beginning of the 19th century such a phenomena were explained by postulating the

existence of a substance termed caloric, an elastic fluid found in every body

In the caloric theory of heat, the temperature of a substance was considered to be determined by

the quantity of caloric gas which it contained, and two bodies of differing temperature, when

placed in contact with one another, came to an intermediate common temperature as the result of

caloric flowing between them

Body at high temperature contained more caloric and the one at a low temperature had only

little caloric

Relationship between work & heat

The relation between heat and work was first suggested in 1798 by Count Rumford

During the boring of cannon at the Munich Arsenal, noticed that the heat produced during the

boring was roughly proportional to the work performed during the boring

Until then heat had been regarded as being an invisible fluid called caloric which resided

between the constituent particles of a substance.

Rumford’s observation that heat production accompanied the performance of work was

accounted for by the caloric theory as being due to the fact that the amount of caloric which

could be contained by a body, per unit mass of the body, depended on the mass of the body

by the boring) contained less caloric per unit mass

than did the original large mass of metal, and thus,

in reducing the original large mass to a number of

smaller pieces, caloric was evolved as sensible heat

Relationship between work & heat

Rumford then demonstrated that when a blunt borer was used (which produced very few metal

turnings), the same heat production accompanied the same expenditure of work

production in this case as being due to the action

of air on the metal surfaces during the

performance of work.

when Humphrey Davy melted two blocks of ice by

rubbing them together in a vacuum

In this experiment the latent heat necessary to melt the ice was provided by the mechanical work

performed in rubbing the blocks together.

Adiabatic work – Joules Experiments

When a closed system is completely surrounded by an adiabatic boundary and the system is

coupled with the surroundings so that work can be done, then the work is called Adiabatic

work

Adiabatic work – Joules Experiments

Lets take the initial state characterized by thermodynamic

coordinates Pi =1 atm and Ti=287.7K

and the final state by the coordinates Pf =1 atm and Tf = 288.7K

i to f Path I

i to a to b to f Path II

i to c to d to f Path III

system may be transferred from an initial state to final

state i to f by the performance of adiabatic work only

Adiabatic work – Joules Experiments

followed, the adiabatic work is same along all

such paths

immersed in the water

Rotating a paddle wheel immersed in the water

Compressing a cylinder of gas immersed in the

water

Rubbing together two metal blocks immersed

in the water

Adiabatic work – Joules Experiments

Joule conducted experiments in which work was performed in a certain quantity of

adiabatically contained water and measured the resultant increase in the temperature of the

water.

If friction in mechanism is

negligible, the work done

by the paddle wheel on the

water equals the change of

potential energy of the

weights.

Rotating a paddle wheel immersed in the water Passing electric current through a coil

immersed in the water

As the weights fall at constant speed,

they turn a paddle wheel, which does Electrical work is done on the system by the

work on water. generator, which is driven by the falling weight.

A direct proportionality existed between the work done and the resultant increase in temperature

and that the same proportionality existed no matter what means were employed in the work

production

Adiabatic work – Joules Experiments

From the Joules experiments, we can generalize and frame a restricted statement called the

First law of Thermodynamics

If a closed system is caused to change from an initial state to a final state by adiabatic means

only, then the work done on the system is the same for all adiabatic paths connecting the two

states

In Mechanics, in moving an object from one point to another point in gravitational field, in the

absence of friction the work done depends only on the positions of the two points and not on the

path through which the body was moved

For a conservative force, there exists a function of the space coordinates of the body whose final

value minus initial value is equal to work done and this function is called potential energy

function

Similarly the work done in moving an electric charge from one point to another in a conservative

electric field is independent of the path and the function is called electric potential function

First law of Thermodynamics

From the Joules experiments, we can generalize and frame a restricted statement called the

First law of Thermodynamics

If a closed system is caused to change from an initial state to a final state by adiabatic means

only, then the work done on the system is the same for all adiabatic paths connecting the two

states

From this restricted statement that we defined, there exists a function of the coordinates of the

thermodynamic system whose value at the final state minus initial state is equal to the

adiabatic work in going from one state to another

Internal Energy

Denoting internal energy function by U, we can write

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

specify the state of the system

Internal Energy

The equilibrium states of a closed hydrostatic system can be described by means of two of the

three thermodynamic coordinates P, V, T

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

coordinates

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

internal energy function

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

If the coordinates characterizing the two states differ from each other only infinitesimally then the

change in the internal energy can be written as dU

Internal Energy

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

Note: The derivatives are not equal because the function U is not the

same in both the cases

is a function of T and V

is a function of T and P

The internal energy is an extensive property of a system (Section F.3) and is mea-

sured in joules (1 J = 1 kg m2 s−2, Section F.4). The molar internal energy, Um, is the

Internal Energy

internal energy divided by the amount of substance in a system, Um = U/n; it is an

intensive property and commonly reported in kilojoules per mole (kJ mol−1).

Molecular interpretation of internal energy

(a) Molecular interpretation of internal energy

A molecule has a certain number of motional degrees of freedom, such as the ability to

A motion

translate (the moleculeofhas

itsacentre

certainofnumber of motional

mass through degrees

space), of freedom,

rotate around itssuch as the

centre of ability

mass, or

to translate

vibrate (as its (the motion

bond lengths of itschange,

and angles centre ofleaving

mass through space),

its centre rotateunmoved)

of mass around its centre

of mass, or vibrate (as its bond lengths and angles change, leaving its centre of mass

unmoved). Many physical and chemical properties depend on the energy associated

with each of these modes of motion. For example, a chemical bond might break if a lot

Accordingoftoenergy becomestheorem,

equipartition concentrated in it, for instance

the average as each

energy of vigorous vibration.

quadratic contribution to the

energy is 1/2The

kT. ‘equipartition theorem’ of classical mechanics was introduced in Section F.5.

According to it, the average energy of each quadratic contribution to the energy is

1

2

kT. As we saw in Section F.5, the mean energy of the atoms free to move in three

the mean energy of theis atoms

dimensions 3

kT free

and theto move

total in three

energy of a dimensionsperfect

monatomic is 32 gas

kT is

and

3 the total

NkT, or 3 energy of a

nRT

2 2 2

monatomic(because

perfect Ngas

= nNis 3/2 NkT, or 3/2 nRT

A and R = NAk). We can therefore write

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

energies of atoms and molecules and interaction amongst atoms and molecules i. e. items (3)

and (4) are considered to be important since changes occurring in them principally contribute

to ΔU.

• Absolute value of the energy is not known. All we can determine is change in internal energy.

• Internal energy will depend on temperature for a material of fixed mass, composition and

structure.

• U is function of Temperature only.

Energy Fig. 1‐4: Forms of energy.

Diathermal Work, Heat & 1st law of Thermodynamics

So far we have been considering processes during which the system undergoes a change of state

through the performance of adiabatic work only

with a flame in contact with liquid

Helium

Now imagine two different experiments performed on the same closed system one

adiabatically and the other diathermically

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

Diathermal Work, Heat & 1st law of Thermodynamics

Now imagine two different experiments performed on the same closed system one

adiabatically and the other diathermically

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

Inorder to be consistent with the law of conservation of energy, we are forced to conclude that

energy has been transferred by means of other than performance of work

This energy which has taken place only by virtue of the temperature difference between the

system and the surroundings is called as Heat

When a closed system whose surroundings are at a different temperature and on which the

diathermic work may be done, then the energy transferred by non mechanical means is

called Heat

Heat and Work

FIRST LAW

Surroundings

Surroundings

Surroundings

Surroundings

Energy

Energy

Energy

Energy

Energy

Energy

Energy

Energy

Energy

Energy

Energy

Energy

hermic

mic

ess Exothermic

process System System

System System

(b) When energy is transferred to the

Fig. 2.3 Fig. 2.4 When a system does work,

Whensurroundings

energy as heat,

is Fig. the

2.3 transfer

transferred When to the

energy it stimulates

is transferred to the orderly motion

Fig. 2.4inWhen

the a system does work,

stimulates randomsurroundings

motion of the as atoms

heat,inthe transfer itWhen

surroundings. For instance, a system

the atoms

stimulates doesinwork,

orderly motion the

surroundings as heat, the

the surroundings. stimulates transfer

Transfer of random

energy from stimulates

shown here may be part of a weight that is

motion of the atoms in it motion

stimulates

surroundings. For orderly motion

instance, the atoms in the

random motion ofthethe

the surroundings to the atoms in Transfer

system makes

surroundings. the of energy from

use being raised. The ordered of the

shown here may be part of a weight that is

of random motion (thermal motion) in the atoms in a falling weightsurroundings.

does work on the For instance, the atoms

surroundings.

surroundings.Transfer of energy from the

the surroundings to the system makes use being raised. The ordered motion of the

of random motion (thermal motion) in the

system. shown here may be part of a weight that

atoms in a falling weight does work on the is

surroundings to the system makes use of

surroundings. being raised. The ordered motion

system. of the

hermic random motion (thermal motion) in the

Heat

ess atoms in a falling weight does work on the

surroundings.

mic Exothermic system.

(b) The molecular interpretation of heat and work

process

ic process(d) In molecular terms, heating is the transfer of energy that makes use of disorderly

he molecular motion(b)inThe molecular interpretation

the surroundings. The disorderlyof heat and

motion work is called

of molecules

This equation is known as the Mathematical formulation of the first law of thermodynamics

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

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

general statement

dQ and dW are not related to the properties of the system but they refer to how the surroundings

interact with the system by means of processes transferring energy

Statement of First law

For an infinetesimal process, the statement is:

dU = δq – δW

Sum of all forms of energy exchanged by a system with its surrounding is equal to the

change in internal energy of the system which is a function of state .

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.

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

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

MM209 - Thermodynamics

Instructor : Aswani Yella

Statement of First law

For an infinetesimal process, the statement is:

dU = δq – δW

Sum of all forms of energy exchanged by a system with its surrounding is equal to the

change in internal energy of the system which is a function of state .

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

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

increase

esent we

The term heat capacity implies that a substance can hold heat

Internal energy, U

n a con- B

, then a but it is false

curve at

The heat

Heat is not a function of thermodynamic state of a system,

A

internal energy is!

So the proper expression should be Internal energy capacity

[2.15]

Temperature, T

e of the

volume Fig. 2.10 The internal energy of a system

Heat Capacity

• In chemical and metallurgical processes, materials get heated or cooled and therefore it is

necessary to know the amount of heat required to heat or amount of heat liberated on cooling

a material over a certain temperature range.

• Different materials require different amounts of heat to get heated through the same

temperature rise. This is because the materials have different heat capacities.

• This is so because of the variation in the crystal structure of the materials and their related

parameters.

Heat Capacity

When heat is absorbed by a system, a change of temperature may or may not take place,

depending on the state of the system, eg., at the melting temperature

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

As both Q and Tf-Ti become smaller, this ratio approaches a limiting value known as the

heat capacity denoted by C

Heat Capacity

Is heat capacity an extensive quantity or an intensive quantity?

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

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

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

Heat Capacity

Each heat capacity of a simple system is function of two variables

Heat Capacity

The mathematical formulation of first law for hydrostatic system is

Heat Capacity

Heat Capacity

volume, no work is done, so energy transferred will be used to expand the

the heat added equals the substance and to increase the internal energy.

increase in Internal energy

Measurement of Heat Capacity

The unit of heat found most convenient was called calorie defined as the heat required to raise

the temperature by 1oC in a system of 1g of water

Later on it was found out that heat necessary to change 1g of water from 0 to 1oC was

different from that of the heat required to go from, say 30 to 31oC.

When the measurements became precise the calorie is defined as the heat needed for 1g of

water to go from 14.5oC to 15.5oC

water per unit mass of water in going from

14.5oC to 15.5oC was called the mechanical

equivalent of heat, which was measured to be

4.1860 J/cal

Measurement of Heat Capacity

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

54 2 THE FIRST LAW

Oxygen

leads is al

A constant-volume bomb calorimeter. The ‘bomb’ is the input

elect

central vessel, which is strong enough to withstand high Bomb circu

pressures. Sample

under

known) is the entire assembly shown here. pressure

We

To ensure adiabaticity, the calorimeter is immersed in a Water cons

water bath with a temperature continuously readjusted to ∆

that of the calorimeter at each stage of the combustion.

It fo

Fig. 2.9A constant-volume bomb

(qV >

calorimeter. The ‘bomb’ is the central

vessel, which is strong enough to withstand in fa

Measurement of Heat Capacity

The change in temperature, ∆T, of the calorimeter is proportional to the energy that the reaction

releases or absorbs as heat.

known energy output and determining the calorimeter constant, the constant C in the relation

q = C∆T

The calorimeter constant may be measured electrically by passing a constant current, I, from a

source of known potential difference, ∆φ, through a heater for a known period of time, t, for then

q = It∆φ

often used) that has a known heat output. With C known, it is simple to interpret an observed

temperature rise as a release of heat.

Enthalpy

• If pressure is maintained constant during change of system

from state I to state II the work done

II II

w= ∫ PdV = P ∫ dV = P (VII − VI )

I I

UII – UI = δq – P(VII – VI )

On rearranging these terms

(UII + PVII ) - (UI + PVI ) = δq

Or HII - Hi = ΔH = δq

Where H = U + PV is called enthalpy. The heat content at

constant pressure is called enthalpy.

Enthalpy

• Enthalpy is a state property but heat is not.

As we know H = U + PV

dH = dU + PdV + VdP

As U is a function of state so one can write

⎛ ∂U ⎞ ⎛ ∂U ⎞

dU = ⎜ ⎟ dP + ⎜ ⎟ dV

⎝ ∂ P ⎠V ⎝ ∂V ⎠P

⎡ ⎛ ∂U ⎞ ⎤ ⎡ ⎛ ∂U ⎞ ⎤

Hence dH = ⎢V + ⎜ ⎟ ⎥ dP + ⎢ P + ⎜ ⎟ ⎥ dV

⎣ ⎝ ∂ P ⎠V ⎦ ⎣ ⎝ ∂V ⎠P ⎦

= M dP + N dV (Say)

Enthalpy

⎡ ⎛ ∂U ⎞ ⎤ ⎡ ⎛ ∂U ⎞ ⎤

M = ⎢V + ⎜ ⎟ ⎥ , N = ⎢P + ⎜ ⎟ ⎥

⎣ ⎝ ∂ P ⎠V ⎦ ⎣ ⎝ ∂V ⎠P ⎦

⎛∂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

⎜⎜ ⎟⎟ = ⎜⎜ ⎟⎟ + ⎢ ⎥

⎝ ∂ P ⎠T ⎝ ∂ P ⎠T ⎣ ∂ P ⎦T

(PV) = 0

Enthalpy

⎛∂H⎞ ⎛ ∂U ⎞

⎜⎜ ⎟⎟ = ⎜⎜ ⎟⎟ = 0

⎝ ∂ P ⎠T ⎝ ∂ P ⎠T

at constant temperature.

Similarly, enthalpy is independent of volume.

Hence H is a function of T only for the fixed mass

of the substance.

Internal Energy Vs Enthalpy

• Internal energy is all that energy stored in the system. But, What does enthalpy

mean? This can best illustrated by the example of calcination of calcium carbonate

and calcium silicate.

Ca2SiO4 = 2CaO + SiO2

CaCO3 = CaO + CO2

• The enthalpy change of the process will be equal to invested bond energy to break

the bond between CaO and SiO2 or internal since both CaO and SiO2 are solids.

• But in the 2nd case CO2 is a gas then breaking of one mole of CaCO3 results in the

formation of 22.4 ltrs. of CO2.

• Because of the generation of 22.4L of CO2, expansion in volume will take place.

• In this process of expansion, the system will do work equivalent to ∫ PdV as

mechanical work on the surrounding.

Internal Energy Vs Enthalpy

• Hence in addition to the requirement of energy for breaking the bond of

CaO-CO2 additional energy equivalent to ∫ PdV will have to be supplied to

the system making a total of U + ∫ PdV and this is the enthalpy change of

the system on calcination.

• For chemical processes where there is no significant change in volume as

in

Ca2SiO4 = 2CaO + SiO2

• The ∫ PdV is practically absent and U and H are almost the same.

• In chemical and metallurgical world, even if term ∫ PdV is absent, it

worthwhile to refer to H which is more appropriate.

Heat Capacity

From the mathematical definition of enthalpy, we can write

H = U + PV

dH = dq + VdP

At a constant Pressure dP =0

⎜ ⎟ =⎜ ⎟

⎝ dT ⎠ p ⎝ dT ⎠ p

Heat Capacity

⎛δ q ⎞ ⎛ ∂H ⎞

CP = ⎜⎜ ⎟⎟ = ⎜⎜ ⎟⎟

⎝ ∂ T ⎠P ⎝ ∂ T ⎠P

Since at constant pressure δq = dH. Further we can write

dH = CP dT

Or H T2 − H T1 =

T2

C P dT

∫ T1

pressure also besides raising temperature

Interrelationship of CP and CV

⎛ ∂H ⎞ ⎛ ∂U ⎞ ⎛ ∂ (U + PV ) ⎞ ⎛ ∂U ⎞

C P − CV = ⎜

⎜ ⎟

⎟ ⎜

−⎜ ⎟

⎟ ⎜

=⎜ ⎟

⎟ − ⎜⎜ ⎟⎟

⎝ ∂ T ⎠ P ⎝ ∂ T ⎠V ⎝ ∂T ⎠V ⎝ ∂ T ⎠V

⎛ ∂U ⎞ ⎛ ∂U ⎞ ⎛ ∂V ⎞

= ⎜⎜ ⎟⎟ − ⎜⎜ ⎟⎟ + P ⎜⎜ ⎟⎟

⎝ ∂ T ⎠ P ⎝ ∂ T ⎠V ⎝ ∂T ⎠P

And we know ⎛ ∂U ⎞ ⎛ ∂U ⎞

dU = ⎜⎜ ⎟⎟ dV + ⎜⎜ ⎟⎟ dT

⎝ ∂ V ⎠T ⎝ ∂ T ⎠V

⎛ ∂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

between the+molecules

CV dT within the sample and hence it is called

πT

internal pressure

U

(b) The Joule experiment

When there are no interactions between the molecules, the internal ener

Joule - Thomson effect

When there are no interactions between the molecules, the internal energy is independent of

their separation and hence independent of the volume of the sample

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

+ CV bath. One was filled with air at about 22 atm

and the other was evacuated

hermodynamics to inspect the output of a manipulation like

any recognizable physical quantity. The partial derivative on

on is theMeasured

slope of the

the plot of volume

change against of

in temperature temperature

the (at

property is normally

water tabulated

of the bath the expansion

when aasstopcock coefficient,

was opened

is defined

andasthe air expanded into a vacuum

High pressure Vacuum

gas

Definition of the

No work was done in the expansion

expansion into a [2.42]

coefficient vacuum, so w = 0

A schematic diagram of the

Fig. 2.25

So, whatever change in the internal energy should be observed as the

apparatus heat

used or theintemperature

by Joule an attempt to

tional change in volume

difference that

from the accompanies

first a rise in tempera-

law of thermodynamics measure the change in internal energy

means that the volume of the sample responds strongly to when a gas expands isothermally. The heat

Joule observed no change in temperature

. Table 2.9 lists some experimental values of α. For future absorbed by the gas is proportional to the

Joule - Thomson effect

No energy entered or left the system (the gas) as heat because the temperature of the bath did

not change, so q = 0.

Within the accuracy of the experiment, ∆U = 0 and Joule concluded that U does not change

when a gas expands isothermally and therefore that πT = 0

The heat capacity of the apparatus was so large that the temperature change that gases do in fact

cause was too small to measure

Later Joule and Thomson performed critical experiment in which an adiabatically contained

gas of volume V1 at pressure P1 was throttled through a porous diaphragm to the pressure P2

and the volume V2

Joule - Thomson effect

80 2 THE FIRST LAW

barrier low pr

pressure

Let a gas expand through a porous barrier from one constant

pressure to another and monitored the difference of

temperature that arose from the expansion pi

adiabatic.

pi

implies that ∆U = w.

pi

Insulation Gas at

high pressure

Joule and Thomson observed a lower temperature on the low pressure side, the difference in

Fig. 2.26 The apparatus used for measuring Fig

temperature being proportional to the pressure difference they maintained

the Joule–Thomson effect. The gas expands Jou

through the porous barrier, which acts rep

as a throttle, and the whole apparatus is gas

thermally insulated. As explained in the eit

text, this arrangement corresponds to an fro

THE FIRST LAW

Joule - Thomson effect

Thermocouples Porous Gas at Upstream Throttle Downstream

Here all changes to the gas occur adiabatically,

barrier q low

=0 pressure pressure

implies that ∆U = w. pressure

pi, Vi, Ti

pi pf

Now we need to find out the work done by the gas

to find out the change in internal energy

pi pf

amount of gas from the high pressure side, where the pressure

is Pi, the temperature Ti, and the gas occupies a volume Vi

The gas emerges on the low pressure side, where the same pf, Vf, Tf

pf

pi

amount of gas has a pressure Pf , a temperature

Insulation Gas atT , and

f

high pressure

occupies a volume Vf.

Fig. 2.26 The thermodynamic basis of

Fig. 2.27

the Joule–Thomson effect. The gas expands Joule–Thomson expansion. The pistons

The pistons represent thethrough

upstream and barrier,

the porous downstream gases,

which acts which maintain

represent constant

the upstream pressures

and downstream

either side of the throttleas a throttle, and the whole apparatus is gases, which maintain constant pressures

thermally insulated. As explained in the either side of the throttle. The transition

THE FIRST LAW

Joule - Thomson effect

Thermocouples Porous Gas at Upstream Throttle Downstream

Lets say that the gas on the left is compressed

barrier isothermally

low pressure pressure

by the upstream gas acting as a piston pressure

pi, Vi, Ti

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

2.12 THE2.

So the isothermally

work done on by

the the

gas upstream

will be gas acting as a piston. The relevant pressure is pi and

isothermally

the volumeby isothermallyfrom Vby

the upstream

changes the

gas upstream

acting as gas acting The

a piston. as a piston.

relevant The relevantispressure

pressure pi and is pi and

i to 0; therefore, the work done on the gas is

the volume changes the volumefrom changes from Vi to 0;

Vi to 0; therefore, thetherefore,

work done the onwork thedone on the gas is

gas is

w1 = −pi(0 − Vi) = piVi pi pf

w1 = −pi(0 − Viw )= 1 =p−pVii(0 − Vi) = piVi

Enthalpy, H

i

The gas expands isothermally on the right of the barrier (but possibly at a different

The gasThe constant

gas expands

expands The

temperature)

isothermally gasonexpands

against

isothermally the right isothermally

theof

on pressure

the right

the onthe

pof the

f provided

barrier, right

by of

butbarrier the the barrier

downstream

(but possibly (but atpossibly

gas aact-

differentat a differen

ingconstant

at a different

constant constant

as temperature)

a piston temperature temperature)

to be driven out.the

against

against The

the against

volume the

changes

pressure

pressure pressure

from 0pby

pfPprovided f provided

to V

the

f the by

, sodownstream thedone

work downstream

gas act- gas act-

f

provided on the

ingbyasthe gas in

downstream

a piston ing

this as a

stage

to be driven piston

is

gas acting to be

out.asThe driven

a piston out.

volumeto be The

changesvolumefrom changes

0 to Vfrom , so 0 to

the V , so the work done

pfwork

, Vff, Tf done

f pf

driven on

outthe w on the gas in this stage

Gas is

at

pi

2 = −pf (Vf − 0) = −pfVf

gas in this stage is

Insulation

high pressure

w2 = −pf (Vf − 0) = −pfVf

wThe

2 = −p

totalf

work

(V f − done

0) = −ponfV the

f

gas is the sum of these two quantities, or

w = w + wThe

The total work done = ptotal

Fig. 2.26

i on

i the −work

V The V done

papparatus

f f gaseffect.

is the

onforthe

used gas is the sum

measuring Fig.of

2.27these two quantities,

The thermodynamic basisorof

1 2 Joule–Thomson

the Thesum of these two

gas expands quantities,expansion.

Joule–Thomson or The pistons

It follows that w change

through

the 1+

= wthe porous

of =barrier,

piVi −energy

w2internal pfVf acts

which of the gas asrepresent

it movesthe upstream andfrom

adiabatically downstream

w = w1 + w2 =aspaiV − p

throttle,

i V

fand f the whole apparatus is gases, which maintain constant pressures

one side of the barrier

Itthermally to the

followsinsulated. other

that theAschange is ofininternal

explained the energy

eitherofside

theofgas as it moves

the throttle. Pressure,

adiabatically

The transition from

= −p

w2 the f (Vf − 0) = −pfVf by the downstream gas act-

Enthal

constant temperature) against pressure pf provided

The total work done on the0 to

gas issothe sumdone

of these two quant

Joule - Thomson effect

ing as a piston to be driven out. The volume changes from

The total work done on the gas is the

on the gas in this stage is w = w + w = p V − p V

V , the work

f sum of these two quantities, or

w = w1 1+ w2 =2 piVii − ipfVf f f

w2 = −pf (Vf − 0) = −pfVf

It follows that the change of internal energy of the gas as it mo

The work

The total changedone on It

thefollows

of internal energy ofthat

gas is the the the

sumgas change

ofas twoofquantities,

it moves

these internal orenergy

adiabatically of the

from one side gas asbarrier

of the it moves

to adia

the other is oneside

one sideofofthethe barrier

barrier to the

to the other

other is is

w = w1 + w2 = piVi − pfVf

U −−UU= =ww

U

ff i i = p=Vp V

− p−Vp V

It follows that the change of internal energy ofi the

ii i f f f f

gas as it moves adiabatically from

one side of the barrier toReorganization

the other is

Reorganization of ofthis expression

this expressiongivesgives Pressure,

Reorganization of this expression gives p

Uf − Ui = w = piVi − pfVf U + p V = U + p V

fUf + pfVf = Ui + piVi or or Hf = H

f f i i i Hi

f = Hi

Reorganization of this expression

Therefore,gives

the expansion occurs without change of enthalpy.

Fig. 2.28 The iso

Uf + pfVf = Ui + piVi Therefore,

or Hf =the

Hi expansion occurs without change of enthalpy.

coefficient is the

respect to chang

Therefore, the expansion

The transition from theoccurs without

top diagram change

to the of diagram,

bottom enthalpy.which represents the passage temperature

of a bei

The property measured in the experiment is the

given amount of gas through the throttle, occurs without change of enthalpy ratio of the temperat

theThe

change property measured

of pressure, ∆T/∆p. inAdding

the experiment

the constraintis the ratio Porous

of enthal

of constant the te

He

he property measured the in

limitthe experiment

of small ∆p

the change of pressure, ∆T/∆p. Adding the constraint of constan

is the

impliesratio of

thatthe temperature

the change

thermodynamic to

quantity measure

plug

change of This

pressure, ∆T/∆p.

coolingwhich

by isenthalpic

Adding expansion is now called

the constraint the Joule–Thomson

ofcoefficient,

constant µ

enthalpy andeffect.

taking

the

imit of small ∆p implies

limitis

that

the

of

the

small ∆p

Joule–Thomson

thermodynamic

implies that

quantity

the . In other

thermodynamic

measured

words, the

is (∂T/∂p)Hto

physicalm

quantity

, the change in p

i

of µ is that

whichcoefficient, it is the ratio

is the Joule–Thomson of the change in temperature

µ. In other words, the p

ch is the Joule–Thomson µ. In other words, coefficient,

the physical interpretation

a gas expands under conditions that ensure there is no changeGas in enthal

of of

is that it is the ratio µTheis that

the changeit is the ratio

in temperature oftothe change

the change in temperature

in pressure

modern method of measuring µ is indirect, and involves m

when to flow

the cha

s expands under conditions that ensure there is no change in enthalpy.

w2 = −pf (Vf − 0) = −pfVf

The total work done on the gas is the sum of these two quantities, or

w = w1 + w2 = piVi − pfVf

It follows that the change of internal energy of the gas as it moves adiabatically from

The property measured in the experiment

one sideis

of the ratio of

the barrier theother

to the temperature

is change to the change of

pressure, ∆T/∆p Uf − Ui = w = piVi − pfVf

Reorganization of this expression gives

f U +pV =U +pV

f f i i i for iH =H

Adding the constraint of constant enthalpy, implies that the thermodynamic quantity measured

Therefore, the expansion occurs without change of enthalpy.

is (∂T/∂p)H which is the Joule–Thomson coefficient, µ.

The property measured in the experiment is the ratio of the temperature change to

The physical interpretation of the

µ ischange

that itofispressure,

the ratio∆T/∆p.

of theAdding

changethein

constraint of constant

temperature to theenthalpy

changeand

intaking

the limit of small ∆p implies that the thermodynamic quantity measured is (∂T/∂p)H,

pressure when a gas expands under conditions that ensure there is no change in enthalpy

which is the Joule–Thomson coefficient, µ. In other words, the physical interpretation

of µ is that it is the ratio of the change in temperature to the change in pressure when

a gas expands under conditions that ensure there is no change in enthalpy.

The modern method of measuring µ is indirect, and involves measuring the isothermal Joule–

The modern method of measuring µ is indirect, and involves measuring the

Thomson coefficient, the quantity

isothermal Joule–Thomson coefficient, the quantity

A ∂H D

µT = B E Definition of the isothermal

[2.52]

C ∂p F T Joule–Thomson coefficient

(Fig. 2.28). Comparing eqns 2.51 and 2.52, we see that the two coefficients are related by

µ T = −Cp µ (2.53)

Reorganization of this expression gives

Uf + pfVf = Ui + piVi or Hf = Hi

Therefore, the expansion occurs without change of enthalpy.

The property measured in the experiment is the ratio of the temperature cha

the change of pressure, ∆T/∆p. Adding the constraint of constant enthalpy and

⎛ ∂H ⎞ ⎛ ∂H ⎞

dH the

= ⎜ limit

⎟ dP + ⎜ ∆p

of small ⎟ implies

dT that the thermodynamic quantity measured is (∂T

⎝ ⎠ ⎝ ⎠

∂P isT the Joule–Thomson

which ∂T P coefficient, µ. In other words, the physical interpre

of µ is that it is the ratio of the change in temperature to the change in pressure

aCp ⎛ ∂H ⎞ under conditions that ensure there is no change in enthalpy.

gas=expands

⎜ ⎟

The⎝ ∂Tmodern

⎠P method of measuring µ is indirect, and involves measurin

isothermal Joule–Thomson coefficient, the quantity

µT = B E Definition of the isothermal

C ∂p F T Joule–Thomson coefficient

⎛ ∂T ⎞ ⎛ ∂H ⎞

−C p ⎜ ⎟ = ⎜ ⎟

⎝ ∂P ⎠ ⎝ ∂P ⎠T

whichH is the slope of a plot of enthalpy against pressure at constant tempe

(Fig. 2.28). Comparing eqns 2.51 and 2.52, we see that the two coefficients are rela

µ T = −Cp µ

To measure µ T , the gas is pumped continuously at a steady pressure through

exchanger, which brings it to the required temperature, and then through a p

plug inside a thermally insulated container. The steep pressure drop is measur

the cooling effect is exactly offset by an electric heater placed immediately af

plug (Fig. 2.29). The energy provided by the heater is monitored. Because ∆H =

Joule - Thomson effect

Real gases have non-zero Joule–Thomson coefficients.

Depending on the identity of the gas, the pressure, the relative magnitudes of the attractive and

repulsive intermolecular forces, and the temperature, the sign of the coefficient may be either

positive or negative

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

expansion

Gases that show a heating effect (µ < 0) at one temperature show a82cooling effect

2 THE FIRST LAW (µ > 0) when

the temperature is below their upper inversion temperature, TI 600

Heating

Heatin

U

Nitrogen

µ>0 in

Temperature, T/K

400

For a given pressure, the temperature must be below a certain

Temperature, T

te

µ> 0

value if cooling is required but, if it becomes too low, the Cooling

Cooling µ<0 L

boundary is crossed again and heating occurs. 200 in

te

Hydro

Helium

0

Pressure, p 0 200

Pressure,

Fig. 2.30 The sign of the Joule–Thomson

coefficient, µ, depends on the conditions. Fig. 2.31 The inversion tempe

Joule - Thomson effect

For a perfect gas, µ = 0; hence, the temperature of a perfect gas is unchanged by Joule–

Thomson expansion.

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

Adiabatic Process

adiabatic process.

dV

CV dT = − R T

V

Or

CV dT dV

=−

R T V

Integration of this equation under the limiting

condition

V = Vi at T = Ti

And

V = Vf at T = Tf

Adiabatic Process

Expression CV Tf Vf

ln = − ln

C P − CV Ti Vi

Or T f V f γ −1 = Ti Vi γ −1 where CP

γ =

CV

Or TV γ −1

= Const Or

PV γ = Const

Or dH = dU + P dV + V dP

As dU = - P dV

So dH = V dP

Adiabatic Process

Pf Vf

ΔH = ∫ V dP = − γ ∫ P dV

Pi Vi

This on integration lead to the expression

γ −1

γ Pi Vi ⎡⎢⎛⎜ Vi ⎞ ⎤

ΔH = ⎟ − 1⎥

γ −1 ⎢⎜⎝ V f ⎟

⎠ ⎥

⎣ ⎦

Adiabatic Process

be deduced as follows

V2 V2 dV

w= ∫ PdV = m ∫

V1 V1 Vγ

⎛ V21− γ − V11− γ ⎞

= m⎜⎜ ⎟⎟

⎝ 1 −γ ⎠

Or

P2V2 − P1V1

w=

1− γ

Where

P V γ = m = a const.

Polytropic Process

n

PV = const.

The work done in this process is similar to adiabatic process but

γ ≠n

PiVi − Pf V f

w=

n −1

n −1

PiVi ⎡⎢⎛⎜ Vi ⎞ ⎤

=− ⎟ −1⎥

n − 1 ⎢⎜⎝ V f ⎟

⎠ ⎥

⎣ ⎦

Polytropic Process

Internal energy can also be expressed in terms of P and V as follows:

Tf

ΔU = − CV ∫ dT = − CV (T f − Ti )

Ti

⎛ Pf V f PV ⎞ C P V ⎡ Pf V f ⎤

= CV ⎜⎜ − i i ⎟⎟ = V i i ⎢ − 1⎥

⎝ R R ⎠ R ⎣ PiVi ⎦

n −1

⎡

CV Pi Vi ⎢⎜ V i ⎟

⎛ ⎞ ⎤

= − 1⎥

⎜

R ⎢⎝ V f ⎠ ⎟ ⎥

⎣ ⎦

From the first law heat exchanged q is obtained as

n −1

[CV (n − 1) − R] Pi Vi ⎡⎛ V ⎞ ⎤

q= ⎢⎜ i ⎟ −1⎥

R (n +1) ⎢⎜⎝ V f ⎟

⎠ ⎥

⎣ ⎦

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

process.

Polytropic Process

ΔH = ΔU + (Pf V f − Pi Vi )

Substituting the expression for ΔU in above expression

n −1

[CV + R] Pi Vi ⎡⎛⎜ Vi ⎞ ⎤

ΔH = ⎢ ⎟ −1⎥

R ⎢⎜⎝ V f ⎟

⎠ ⎥

⎣ ⎦

Or

n −1

C P Pi Vi ⎡⎛⎜ Vi ⎞ ⎤

ΔH = ⎢ ⎟ −1⎥

R ⎢⎜⎝ V f ⎟

⎠ ⎥

⎣ ⎦

Above equation show that for n = 1 i.e. isothermal process with ideal gas , both

change in internal energy and enthalpy are equal to zero.

Summary of Thermodynamic

Processes

Process characteristics P-V-T Work done Heat exchange

relationship

Isothermal dT = 0 PV = const RT ln (Vf / Vi) RT ln (Vf / Vi)

Isochoric dV = 0 P/T = const 0 Cv (Tf – Ti)

Isobaric dP = 0 V/T = const Pi(Vf – Vi) Cp (Tf – Ti) +

Pi(Vf – Vi)

Adiabatic q=0 PVγ = const (PfVf - Pi Vi) / (1- γ) 0

polytropic - PVn = Const (PfVf - Pi Vi) / (1- n) Cv (Tf – Ti).

(γ - n)/(1-n)

MM209 - Thermodynamics

Instructor : Aswani Yella

⎛ INTRODUCTION

∂ G′ ⎞the distinction

o156introduced ∂S′THE

⎛ TO between

⎛ CP ⎞ the heat

⎞ THERMODYNAMICS capacity per

OF MATERIALS, SIXTHmole

EDITION

⎜ ⎟ = −⎜ ⎟ = −⎜ ⎟ (5.12)

e heat capacity

∂T 2 of the⎝ ∂entire

T ⎠ substance

⎝ T ⎠ as follows:

⎝

Variation ⎠P of heat P

Capacity with Temperature

in which c p and c v are, respectively, the constant-pressure and constant-volume

thatCheat

nmolar the = ncv dTand

v dTfollowing

capacities theorinternal

holds for dU = cv and

theenergy dT enthalpy areheat

constant-volume (2.6a)

givencapacity:

for 1 mole of the

substance. Integration of Equation 2.6b between the states (T 2 ,P ) and (T 1 ,P ) gives

C dT2 = between

the difference

p⎛ nc dT the molar

∂ A′ ⎞ p ⎛ ∂S′ ⎞

dH = c ofdTthe two states as

or enthalpies (2.6b)

⎛ CV ⎞p

⎜ 2 ⎟ = −⎜ ⎟ = −⎜ ⎟ T2

⎝ ∂T ⎠V ∂T T

⎝∆H = ⎠HV(T2 , P )⎝− H (T⎠1, P ) = ∫T1

c p dT (6.1)

so introduced

from which it isthe

Knowledge ofdistinction

seen the between

thatvariation

knowledgeof of the

cp the

with heat capacity

temperature

variation per mole

is required

of c p with 155

for the

temperature is

erequired

heatdetermination

capacity

for the of the

of entire substance

the temperature

determination of as follows:

dependence

the temperature of the enthalpy.

dependence of the enthalpy.

Similarly, integration of Equation 2.6a between T 2 and T 1 at constant volume shows

Cv dT = nc

that knowledge of the

v dT

variation

or of cdU = ctemperature

v with

v dT

is required for the determina-

(2.6a)

tion of the temperature dependence of the internal energy. Later in this chapter, we

will show that this is also the case for the determination of the temperature depen-

Cofp dT

denceIntegration

= nc pof

entropy. Thus,

or dH

dTdUbybetween T2 =

knowing the andc pT

dT1 at constant

temperature volume

dependence

(2.6b)

shows

at constant that

pressure

knowledge

(volume) ofcapacity

of the heat the variation of cv with

as a function temperature

of temperature, weiswill

required

know theforGibbs

the

determination

(Helmholtz) of change

free energy the temperature dependence

with temperature, of the

which will internal

enable energy.

us to determine

the equilibrium state of the system in question.

155

Variation of heat Capacity with Temperature

In 1819, as a result of experimental measurements, Dulong and Petit

introduced an empirical rule which states that the molar heat capacities

(cv) of all solid elements have the value 3R

have values which are close to 3R, subsequent experimental measurement

showed that the heat capacity usually increases slightly with increasing

temperature and can have values significantly lower values than 3R at low

temperatures

Variation of heat Capacity with Temperature

HEAT CAPACITY, ENTHALPY, ENTROPY 157

25

20 Pb

cv, joules/mole.K 15 Cu

10 Si

5

Diamond

0

0 50 100 150 200 250 300

Temperature, K

Although leadFigure

and 6.1 The constant-volume molar heat capacities of Pb, Cu, Si, and diamond as func-

copper closely

tions of obey Dulong and Petit’s rule at room temperature, the constant

temperature.

volume heat capacities of silicon and diamond are significantly less than 3R at room temperature

each of the 3n oscillators is not influenced by the behavior of its neighbors, and

assigned a single frequency ν to each of the oscillators. Such a system of quantum

oscillators is now called an Einstein solid (sometimes an Einstein crystal ).

For a fixed frequency of vibration, the energy levels of a quantum harmonic

Notice the significant decrease in the heat capacities at low temperatures.

oscillator take values of the i th energy level as

(1 − exp( ))

kT

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

differ from substance to substance.

• The last term is the smallest and therefore often

ignored.

• In some cases, such as liquid metals, both bT and

cT-2 are usually ignored.

• The above expression is also valid for diatomic

and polyatomic gases as well.

The experimentally

experimentally measuredmeasured

variation variation of the constant-pressure

of the constant-pressure molar heat molar he

acity Variation

The experimentally

of a material

of a material of

with temperature

with heat

measured

temperatureCapacity

variation

is normally

is normally anwith

oftothe

fitted Temperature

constant-pressure

expression

fitted to an molar heat

ofexpression

the form of the for

capacity of a material with temperature is normally fitted to an expression of the form

c

c p = a + bT + cc

ccpp ==Ta ++bT

2

bT++ 2 2

TT

be It

noted

Thisthat

should bethe

expression analytical

noted isthat

onlythe expression

applicable is only

in theexpression

analytical stated applicable

temperature

is onlyrange inover

thewhich

applicable stated thetem-

in the values of

stated tem-the

hould

range be

heat

over

perature noted

rangethat

capacity

which thethe

were

over values

whichanalytical

measured andthe

of

the

fit to

values expression

heatthe equation

of capacity is only

were

the heat capacity applicable

measured

were and fit

measured inand

thefitstated

to to tem

ature

tion.therange

For over

example,

equation. Forwhich

ZrO theZrO

2 exists

example, values ofasthe

as2 monoclinic

exists α -ZrOcapacity

heat

monoclinic 2 from

α -ZrOroom weretempera-

measured and fit

2 from room tempera-

478 K and

equation.

ture as

For

to 1478 tetragonal

Kexample, β -ZrO

ZrO

and as tetragonal βthe

2 2inexists

-ZrO range

2as of range

temperature

in monoclinic

the α 1478–

-ZrO

of temperature 2670

from

1478– K,room

2670 K,temper

Eg: ZrO 2 exists as monoclinic α-ZrO 2 from room temperature to 1478 K and

2 as tetragonal β-

polymorph

to and

1478 each

ZrO 2K

has its

andrange

the asown

in polymorph hasequation

its own

tetragonal

of temperature βgiving

equation

-ZrO

1478–2670 the

in

K, variation

giving

the

and the

range

each ofofitstemperature

variation

polymorph heat

has capacity

ofitsits

own heat capacity

1478– 2670 K

equation

2

with

perature. temperature.

giving the variation of its heat capacity with temperature.

each polymorph has its own equation giving the variation of its heat capaci

h temperature.α − ZrO 2 c = 69.62 −37.53 × 10 −3 T − 14

+ 2 × 10 5 T −2 J/K ⋅ mole

5 .0−6

α − ZrO c = 69.62 + 7.53 × 10 T − 14.06 × 10 T J/K ⋅ mole

p

2 p

over the temperature range 298–1478 K

over the temperature range 298– 1478 K, and

α −range

temperature c p =1478

ZrO2298– 7.53 × 10 T − 14.06 × 105 T −2 J/K ⋅ mole

K, +and

69.62 −3

r the temperatureβ range

− ZrO2c p = 74.48 J/K ⋅ mole

298– 1478 K, and from 1478 to 2670 K

from 1478 to 2670 K. At the transition temperature, the heat capacity drops by about

8 to5.6

2670

At

J/K⋅ K.

the At the

transition

mole. transition

temperature,

In fitting the temperature, the

the heat capacity

analytical heat

drops

expression to capacity

bythe

about drops

5.6 J/K

measured by

mole.

heat about a , b ,

capacities

mole.and

In cfitting the analytical

β expression

− ZrO2c p to = 74

the

.48 J/K ⋅ mole

measured heat capacities a , b ,

, each have nonzero values in the expression for α -ZrO 2 , whereas the molar heat

Variation of heat Capacity with Temperature

HEAT CAPACITY, ENTHALPY, ENTROPY 163

140

Si3N4 Al2O3

120

100

MoSi2

cp, joules/mole.K

80

60 AlN

Cu(l)

40 O2

20 Cu

C(graphite)

C(diamond)

0

300 500 700 900 1100 1300 1500

Temperature, K

and compounds. of the constant-pressure heat

Figure 6.4 The variations, with temperature, of the constant-pressure heat capacities of sev-

eral elements

b-CaF2

120

CaF2(l)

100 a-CaF2

a-CaC

0

300 500 700 900 1100 1300 1500

Temperature, K

Figure 6.4 The variations, with temperature, of the constant-pressure heat capacities of sev-

eral elements and compounds.

140

b-CaF2

120

CaF2(l)

100 a-CaF2

a-CaC2

cp, joules/mole

a-ZrO2

80

b-CaC2 b-ZrO2

60

g-Mn d-Fe

d-Mn

a-Fe

40

a-Mn g-Fe Fe(l)

b-Mn Mn(l)

20

0

300 500 700 900 1100 1300 1500 1700 1900

Temperature, K

The variations,

Figure 6.5 Thewith temperature,

variations, ofconstant-pressure

with temperature, of the the constant-pressure

molar heat capacities

of some elements which exhibit allotropy and some compounds which exhibit

molar heat

capacities of some elements which exhibit allotropy and some

polymorphism.

Variation of heat Capacity with Temperature

If specific heat values of compounds are not known from

experimentation, it can be approximately evaluated by the use of 'Kopp

Rule’ suggested in 1864.

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

per g atom

elements obey Dulong and Petit's law.

out approximate values of specific heats from the specific heat values of

individual components.

The specific heat of solutions is equal to the weighted sum of the

heat capacities of the components.

Variation of Enthalpy with Temperature

equal to the heat supplied to the system (q) at constant

pressure.

• The constant pressure restriction is mostly not important

for example H is not function of P for ideal gases.

• Energies of solid and liquids are hardly affected by some

changes in pressure due to their very small molar

volumes. In other words, the VdP term is negligible.

• In most metallurgical and materials processing, gases are

ideal and pressure is maximum a few atmosphere.

Therefore ΔH = q approximation is quite all right.

Thermochemistry

• It may be defined as the branch of science which deals with the study of

heat exchanges associated either with chemical reaction or physical

changes in the state of matter such as melting, sublimation or evaporation

etc.

(Exothermic reaction)

• The release of heat signifies a decrease in the enthalpy of a system, we can

now see that an exothermic process is one for which ∆H < 0

• If heat is absorbed during a chemical reaction it is denoted by +ve sign

(endothermic reaction).

• Because the absorption of heat results in an increase in enthalpy, an

endothermic process has ∆H > 0

Thermochemistry

Changes in enthalpy are normally reported for processes taking place

under a set of standard conditions.

enthalpy for a process in which the initial and final substances are in

their standard states:

is its pure form at 1 bar.

Eg: the standard state of liquid ethanol at 298 K is pure liquid ethanol at

298 K and 1 bar; the standard state of solid iron at 500 K is pure iron at

500 K and 1 bar

difference between the products in their standard states and the reactants

in their standard states, all at the same specified temperature

That is, the solidification of liquid A , whose equilibrium solidification temperature

Thermochemistry

(which is also the equilibrium melting temperature) is T 2 . The segment cd is the

change in enthalpy at the equilibrium liquid-to-solid transformation; that is, it is

the heat of solidification and can be seen to be H S (T 2 ) – H L (T 2 ) < 0 (exothermic). A

Absolutesupercooled

value of enthalpy change

liquid can of atosubstance

transform a solid at is

T 1not

. Theknown. Only weofcan

molar enthalpy measure are

transforma-

changestion at this temperature can be determined, since the enthalpy is a state function.

of enthalpy.

Thus,

( in) temperature

( ) and/or( composition

)

∆H b → a = ∆H b → c + ∆H c → d + ∆H d → a (i)

can be

graphically represented on an enthalpy–temperature diagram

HL (T2) c

Liquid

b

HL (T1)

Enthalpy

HS (T2) d

d

Soli

HS (T1) a

T1 T2

Figure 6.6 The variation, with temperature, of the molar enthalpies of the solid and liquid

phases of a substance.

Classification of Enthalpy change

• Enthalpy change occur due to various causes.

• Sensible heat: enthalpy change due to change of

temperature of a substance is known as sensible heat. It

is divided into:

• Enthalpy change due to changes in state of aggregation

of substance

• Enthalpy change without any change in aggregation of

the substance

• Heat of reaction

• Heat of mixing

Classification of Enthalpy change

i) Enthalpy change due to changes in state of aggregation of

substance : These are isothermal processes. By convention

enthalpy changes for all isothermal processes are

designated by ΔH. For example,

ΔHm = enthalpy change of one mole of solid due to melting

(i. e. latent heat of fusion per mole )

ΔHv = enthalpy change of one mole of liquid due to

vaporization (i. e. latent heat of vaporization per mole )

Classification of Enthalpy change

Consider a pure substance A, which is undergoing

following changes during heating from 298 to T K

at 298 K at Tm at Tb at T

Tm and Tb are the melting and boiling points of A.Then

Tm Tb

H T − H 298 = ∫ CP ( s) dT + ΔH m + ∫ CP (l ) dT

298 Tm

Tm

+ ΔHV + ∫ CP ( g ) dT

Tb

gaseous A. it is only applicable for pure substance.

Classification of Enthalpy change

aggregation of the substance:

As a universal convention, thermo chemical data

books take sensible heat at 298 K (250C) as zero for

any substance. Hence sensible heat at temperature T,

per mole of a substance is given as:

T

H T − H 298 = ∫ CP dT

298

Classification of Enthalpy change

Putting the expression for heat capacity, we get

T

∫ (a + b T + c T )dT

−2

H T − H 298 =

298

= a (T − 298) + b

2

(T 2 2

)

− 298 − c (T1 − 1

298

)

2 −1

= AT + B T − C T + D

Where A, B, C and D are lumped parameters and functions

of empirical constants a, b, c

Classification of Enthalpy change

Heat of mixing (ΔHmix): This is the change of enthalpy that

occurs when a substance is dissolved in solvent.

This process is generalized as

A (pure) = A (in solution)

This process is also accompanied by a change of enthalpy

(ΔHmix), where

(ΔHmix) = HA (in solution) – HA (pure)

for thermodynamic calculations

Classification of Enthalpy change

Heat of reaction (ΔH): This is the change of enthalpy that occurs

when a reaction takes place. By convention reaction is considered to

be isothermal. Consider the following reaction occurs at

temperature T:

A (pure) + BC (pure) = AB (pure) + C (pure)

Then

ΔH (at T) = ΔHAB (at T) + ΔHC (at T) - ΔHA (at T) - ΔHBC (at T)

of pure AB, BC, A and C, respectively.

Some comments:

• For calculation of enthalpy change, reactions, dissolutions

and phase transformations has been assumed to occur

isothermally. Since enthalpy is a state property, it depends

only on initial and final states and not the path.

• For a reversible isothermal process, the temperature

remains constant all through. If the process is not

reversible, then temperature at the beginning and end of a

process would be same. In between, temperature can vary

significantly.

Hess s Law

It states that the total heat exchanged in a given chemical reaction, which may take place under

constant pressure, volume or temperature is the same irrespective of the fact whether it is

made to take place over a path involving formation of number of intermediate products or

over the one involving the formation of final product from the reactant directly in one stage.

ΔH =ΔH1+ΔH2+ΔHx+ΔHy

The total heat exchanged in a chemical process is the same irrespective of whether the process

occurs in a direct single stage or through multiple stages.

Hess s Law

Eg: Reduction of iron oxide by carbon or carbon-monoxide gas

The reaction can be carried out in one stage as

Fe2O3 + 3C = 2Fe + 3CO

3Fe2O3 + C = 2Fe3O4 + CO

2Fe3O4 + 2C = 6FeO + 2CO

6FeO + 6C = 6Fe + 6CO

thus:

The enthalpy change in reaction (2.4i]) i.e. single stage is gi\,€n by

AH1z.+s1 = 2HreHessQ'a b

and enthalpy change in reactions

s

+ 3Hco - 3Hc- Law

l

Hr".o.

(2.46) are

(2An

(2.48)

= 2HFeooq + Hco - 3H5er9. - H6

AH1z.aal

IHp.+sy - 6Hneo + 2Hco - 2Hresg. - 2Hc (2.4e1

Calculate theAHlz.my=

enthalpy 6Hreof+ formation

6l-lco - 6Hreo of WC from the following(2.50)

- 6Hc

which on addition gives the same equation as inEq. Q'al

data at 25 C

Example : Calculate the enthalpy of forrnation of WC from the follcnrving data at 25 C:

(21 C+ Oa=COz

AHo = -940950 cali g mole

(3) w +'tloz - 'z

wos

AHo = -195700cailgmole

Solution : WC is formed from C and Was

W+ C- WC

and is obtained by addition of equations 2 and 3 and subtracting from this, equation 1

and

the algebric summation of the AHo values give the required enthalpy change as

AHo= AHz+693 -AHr

(-285800)

: -;ff' ;r]ffl"*

2.10 HEAT CAPACITY CALCULATIONS

Heat capacity for any substance is not a fixed value. For the same material it changes

with temperature and the way it changes with temperature varies considerably from

sub-

relationship has to be established experimentally. Howewl

Kirchoff s Law

Utility:

various temperatures, provided the enthalpy is

known at some other temperature, and the heat

capacity of the reactants and products are known in

the range of temperatures under consideration.

Derivation:

whose enthalpy change is ΔH1. Calculate the

enthalpy change ΔH2 at temperature T2.

Kirchoff s Law

The product of this reaction at T2 can be obtained in many

different ways. Let us, however, consider the reaction to be

carried out first by reacting the reactants (x+y) at T1 and then

raising the temperature of the products from T1 to T2 along

ABC.

Kirchoff s Law

The heat absorbed by this process will be

T2

ΔH1 + ∫ CPz dT

T1

raise the temperature of the reactants from T1 to

T2 and then react them together at T2 i. e. along

ADC. The heat absorbed by this process is

T2

ΔH 2 +

∫ (C

T1

Px )

+ C P + dT

y

Kirchoff s Law

According to Hess s law the heats absorbed during the two ways of

producing z must be the same since the initial conditions of the reactants

and final conditions of the products are in each case the same.

T2 T2

ΔH 2 +

∫ (C Px )

+ C P + dT

y

= ΔH1 + ∫ T1

CPz dT

T1

Or ΔH 2 − ΔH 1 = ∫

T2

T1

[C − (C

Pz Px + C Py dT )]

Or T2

ΔH 2 − ΔH 1 = ∫ Δ C P dT

T1

Or T2

ΔH 2 = ΔH 1 + ∫ Δ C P dT

T1

Kirchoff s Law

Since all the terms are known in the right hand of

the equation, ΔH2 can be calculated. We know

T2

ΔH 2 − ΔH 1 = ∫ Δ C P dT

T1

It means the rate of change of enthalpy of a process

or a reaction with temperature is given by the

difference of the heat capacity at constant

pressure of products and reactants taking part in

the reaction ⎛ ∂ ΔH ⎞

⎜⎜ ⎟⎟ = Δ C P

⎝ ∂T ⎠P

Thermochemistry

166 166 INTRODUCTION TO THE

INTRODUCTION THERMODYNAMICS

TO THE OF OF

THERMODYNAMICS MATERIALS, SIXTH

MATERIALS, EDITION

SIXTH EDITION

Convention assigns the value of zero to the enthalpy of elements in

their stable states at 298 K (25°C) and P = 1 atm.

of oneofmole

one mole

of theofcompound

the compound

fromfrom its elements

its elements at 298

at 298 K and

K and P =P1=atm.

1 atm.

ForFor example,

example,

for theforoxidation

the oxidation reaction

reaction

For example, for the oxidation reaction

1) + 1

M(+solid O2( gas) = MO(solid ) at 298 K and P = 1 atm

M(solid ) O ( gas ) = MO( solid ) at 298 K and P = 1 atm

22

2

1

∆H 298 = H MO(s )298 − H M( s )2981−

∆H 298 = H MO(s )298 − H M( s )298 − H2O2H( gO)298

2 ( g ) 298

2

and, since H M,298 and H O2 ,298 are by convention set equal to zero, then

and, since HSince

M,298 and are H

H O2 ,298and

HM,298 by convention set equal to zero, then

O2 ,298 are by convention set equal to zero

∆H 298 = H MO,298

∆H 298 = H MO,298

The variation of heats of chemical reaction (or heats of formation) with temperature

The variation of pressure

at constant heats of chemical reaction (or

can be represented on heats of formation)

an enthalpy– with temperature

temperature diagram, such

at constant pressure

as those can6.7a

in Figure be and

represented on an

b, which are enthalpy–

drawn for thetemperature diagram, such

oxidation reaction

as those in Figure 6.7a and b, which are drawn for the oxidation reaction

1

Pb + O2 = PbO

1

Pb + O22 = PbO

2

The pertinent thermochemical data for this system are listed in Table 6.1.

∆H 298 = H MO,298

Thermochemistry

Figure 6.7b (b) The variation, with temperature, of the enthalpies of (Pb + 1/2O 2 ) and PbO.

The variation of heats of chemical reaction (or heats of formation) with tem

at constant pressure can be represented on an enthalpy– temperature diagr

Table 6.1 Thermochemical Data for Pb, PbO, and O2 as those in Figure 6.7a and b, which are drawn for the oxidation reaction

HPbo(298) = –219,000 J/K

1

Pb + O2 = PbO

The variation of heats of chemical reaction (or heats of formation) with

cp,Pb(s) = 23.6 + 9.75 × 10–3T J/K from 298 K to Tm,Pb

cp,Pb(l ) = 32.4 – 3.1 × 10–3T J/K from Tm,Pb to 1200 K

2

cp,PbO(s) = 37.9 + 26.8 × 10–3T J/K from 298 K to Tm,Pbo The pertinent thermochemical data for this system are listed in Table 6.1.

cp,O2(g) = 29.96 + 4.18 × 10–3T – 1.67 × 105T–2 J/K from 298 K to 3000 K In Figure 6.7a:

temperature diagram

∆Hm,Pb = 4810 J at Tm,Pb = 600 K

Tm,PbO = 1159 K

50

40

• a represents the enthalpy of 1/2 mole of oxygen gas and 1 mole of Pb( s ) at 298 K

(set = 0 by convention). 30

i

• ab represents the variation of H Pb( s ) with temperature in the range 298 ≤ T ≤ 600 K,

T

20 Pb (l)

where H Pb( s ) , T is given by ∫298 c p, Pb( s ) dT .

h

• ac represents the variation of H 1 O2 ( g ) with temperature in the range 298 < T < 10 1/2O 2(g) c

Enthalpy, H, kJ

2

T Pb (s) b

3000 K, where H 1 O2 ( g ) is given by 12 ∫298 c p,O2 ( g ) dT . a

2

• ad is Δ H PbO( s ),298 K = – 219,000 J. 0

• de represents the variation of H PbO( s ) with temperature in the range 298 K ≤ T ≤ –180 e

T

1159 K, where H PbO(s ),T = −219, 000 + ∫298 c p, PbO(s ) dT J .

–190

In Figure 6.7b:

PbO (s

)

–200

• a represents the enthalpy of 1/2 mole of O2( g ) and 1 mole of Pb( s ) at 298 K.

• f represents the enthalpy of 1/2 mole of O2( g ) and 1 mole of Pb( s ) at the temperature T. –210

d

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

–220

300 500 700 900 1100

Temperature, K

(a)

Figure 6.7a (a) The variation, with temperature, of the enthalpies of Pb( s ) , Pb( l ) , 1/2

PbO( s ) .

HPbo(298) = –219,000 J/K

cp,Pb(s) = 23.6 + 9.75 × 10–3T J/K from 298 K to Tm,Pb

Thermochemistry

cp,Pb(l ) = 32.4 – 3.1 × 10–3T J/K from Tm,Pb to 1200 K

cp,PbO(s) = 37.9 + 26.8 × 10–3T J/K from 298 K to Tm,Pbo

cp,O2(g) = 29.96 + 4.18 × 10–3T – 1.67 × 105T–2 J/K from 298 K to 3000 K

The variation of heats of chemical reaction

HEAT CAPACITY, (or heats

ENTHALPY, of formation) with

ENTROPY

∆Hm,Pb = 4810 J at Tm,Pb = 600 K

temperature

Tm,PbO = 1159 K

at constant pressure can be represented on an enthalpy–

50

temperature diagram T T’

40 l

)

• a represents the enthalpy of 1/2 mole of oxygen gas and301 mole of Pb( s ) at+ 1298 /2O K

2(g

Pb

(set = 0 by convention). 20 k

• ab represents the variation of H Pb( s ) with temperature in the 10

range 298

f

≤ Tj ≤ 600 K,

Enthalpy, H, kJ

T

where H Pb( s ) , T is given by ∫298 c p, Pb( s ) dT . a

0

• ac represents the variation of H 1 O2 ( g ) with temperature in the range 298 < T <

2 –180 e

T

3000 K, where H 1 O2 ( g ) is given by 2 ∫298 c p,O2 ( g ) dT .

1

2 –190

• ad is Δ H PbO( s ),298 K = – 219,000 J.

PbO (s

)

• de represents the variation of H PbO( s ) with temperature in the range 298 K ≤ T ≤

–200

T

1159 K, where H PbO(s ),T = −219, 000 + ∫298 c p, PbO(s ) dT J . –210 g

d

–220

In Figure 6.7b: 300 500 700

Temperature, K

900 1100

(b)

• a represents the enthalpy of 1/2 mole of O2( g ) and 1 mole of Pb( s ) at 298 K.

• f represents the enthalpy of 1/2 mole of Figure

O2( g ) and

6.7b 1(b)

mole of Pb( s )with

The variation, at the temperature

temperature, T.

of the enthalpies of (Pb + 1/2O ) a 2

Table 6.1 Thermochemical Data for Pb, PbO, and O2

UCTION TO THE THERMODYNAMICS OF MATERIALS, SIXTH EDITION

hus,

∆H PbO,298 K Thermochemistry

= ∆H (a → f ) + ∆H ( f → g) + ∆H ( g → d )

⎛1 T

⎞ 298

=

∫

⎜ 2 c p,O2 ( g ) +OF

CTION TO THE THERMODYNAMICS

298 ⎝

c p,Pb

∫

( s ) ⎟ dT + ∆HSIXTH

MATERIALS,

⎠

PbO,T +EDITION

c p,PbO(s )dT

The variation of heats of chemical reaction (or heats of formation) with

T

168 = ∆H (a → f ) + TO

INTRODUCTION ∆HTHE → g) + ∆H ( g OF

( f THERMODYNAMICS →MATERIALS,

d) SIXTH EDITION

d thus, temperature

T

⎛1 at constant ⎞ pressure can beCAPACITY,

298 HEAT represented on an enthalpy–

∫ ∫

ENTHALPY, ENTROPY

= temperature

Thus, ⎜ 2 c p,O2 ( g ) + diagram

c p,Pb( s ) ⎟ dT + ∆H

T PbO,T + c p,PbO(s )dT

298 ⎝

= ∆H (a → f ) + ∆H ( f →

T∆H PbO,298 K

∆HgT )=+ ∆∆H ⎠

H298( g+ → d∆) c p dT

= ∆H (a → f ) + ∆H ( f → g298

T

) + ∆298

∫

H (g → d )

50

⎛1 ⎞ T T’

∫ ∫

40

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

c + c T

s ) dT

298 l

∫ PbO,T +

∫

)

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

2(g

298 ⎝ 2 ⎠ T Pb

+

T

∫

1 20 k

and thus, ∆HT = ∆∆H = c+p,PbO( s ) ∆

c p298 −ccpp,dT

Pb ( s ) − c p , O2 ( g ) j

2 10 f

Enthalpy, H, kJ

298

T a

∫

T

∫

0

∆HTin=Table

From the data ∆H 298

6.1,+∆HT ∆

= c∆pHdT

298 + ∆c p dT

298 298 –180 e

where: –190

∆c p = −0.7 + 14.96 ×110 −3 T + 0.85 × 10 5 T −2

∆c p = c p,PbO( s ) − c p,Pb( s ) − c p,O12 ( g ) –200 PbO (

s)

c p = c p,PbO1( s ) −from ( s ) − to c600

p,O ( K

g ) (T

m ,Pb ): –210

2

∆c pthe

In = c prange

, PbO ( s ) − cof s) − c p,O2 ( g ) 2from

p, Pb (temperature 298 to 600 K d

g

2 –220

n Table

From 6.1,

the data in Table 6.1, T

300 500 700 900 1100

∫

Temperature, K

Table 6.1,∆HT = −219, 000 + (−0.7 + 14.96 × 10 −3 T + 0.85 × 10 5 T −2 )dT (b)

298 −3

∆c p = −0.7 + 14.96 × 10

−3 T + 0.855 × 1−02−53T −22

∆c p = −0.=7 −+219 000×−100.7(TT −+298

14,.96 ) +×

0.85 7.148

0 ×T10 (T − 298 2

) 6.7b

Figure (b) The variation, with temperature, of the enthalpies of (Pb + 1/2O 2 ) an

−3 −2

∆c pthus,

= −0in.7the

+ 14 × 1temperature

.96 of 0 T +10.85from

× 10 T 5

and, range 5⎛ 1 ⎞298 to 600 K (T m ,Pb ):

− 0.85 × 10 −

e range of temperature from⎜⎝ T298298 ⎟

to 600

⎠ K (T m ,Pb ): Table 6.1 Thermochemical Data for Pb, PbO, and O2

range of temperature from 298 to

T 600 K (T m ,Pb ):

−3 5 −2

HPbo(298) = –219,000 J/K

∆H 298 = H MO(s )298 − H M( s )298 − H O2 ( g )298

2

⎛1 1 ⎞

− 0.85 × 10 5 ⎜ − ⎟

⎝ T 298 ⎠ Thermochemistry and, since H M,298 and H O2 ,298 are by convention set equal to zero, then

∆H 298 = H MO,298

The variation of heats of chemical reaction (or heats of formation) with tempera

at constant pressure can be represented on an enthalpy– temperature diagram, s

T = 500IfK,

a phase change

this gives ∆ H 500occurs

= – in oneJ, or

217,800 as more

can be of theinreactants

seen Figures or and

6.7b products,

as those in Figure 6.7a and b, which are drawn for the oxidation reaction

K

between the two temperatures at which the reaction

f a phase change occurs in one or more of the reactants or products, between is being Pb + considered,

1

2

O = PbO 2

then theatenthalpies

wo temperatures of transformation

which the reaction of the then

is being considered, phase thechanges

enthalpiesmust of be

The pertinent thermochemical data for this system are listed in Table 6.1.

In Figure 6.7a:

ormation of the phase changes must be considered. In Figure 6.7a, h represents

considered 50

thalpy of 1 mole of Pb( l ) at the melting temperature of 600 K, given as 40

30

i

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

∫

20

temperature of H600 K 10

h

1/2O 2(g) c

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

Temperature, K

(a)

600 T

H Pb(l ),T =

∫

298

c p, Pb( s ) dT + ∆H m, Pb +

∫

600

c p, Pb(l ) dT

Figure 6.7a (a) The variation, with temperature, of the enthalpies of Pb( s ) , Pb( l ) , 1/2O2( g ) ,

PbO( s ) .

ure 6.7b, ajkl represents the variation of the enthalpy of 1 mole of Pb and 1/2

of O2( g ) , and hence, ∆HT ’ is calculated from the cycle

Thermochemistry

ajkl

CAPACITY, representsENTROPY

ENTHALPY, the variation

of the enthalpy of 1 mole of Pb and 1/2

169moles of O2(g), and

CAPACITY, ENTHALPY, ENTROPY 169

hence, ∆HT is calculated from the cycle

HEAT CAPACITY, ENTHALPY, ENTROPY

∆H 298 K = ∆H ( a → d ) = ∆H ( a → j ) + ∆H ( j → k ) + ∆H ( k → l )

∆H 298 K = ∆H ( a → d ) = ∆H ( a → j ) + ∆H ( j → k ) + ∆H ( k → l ) 50

+ ∆H ( l → e ) + ∆H ( e → g ) + ∆H ( g → d ) 40

T T’

+ ∆H ( l → e ) + ∆H ( e → g ) + ∆H ( g → d )

l

)

2(g

30 /2O

where: Pb

+ 1

where: 20 k

Tm ,Pb

⎛ 1 ⎞

∫

j

∆H (a → j ) = +

⎜ p, Pb( s ) 2 pO2 ( g ) ⎟ dT

c c 10 f

Enthalpy, H, kJ

298Tm ,⎝Pb ⎛ 1 ⎠ ⎞ a

∆H (a → j ) =

∫ ⎜c

∆H ( j → k ) = the latent 298

+ c

2 ⎟ dT

p, Pb ( s )

⎝ heat of melting of⎠ Pb at T

pO 2 ( g )

m , Pb = 4810 J

0

–180 e

∆H ( j → k ) = Tthe⎛latent heat

1 of melting

⎞ of Pb at Tm, Pb = 4810 J –190

∆H (k → l ) =

∫ T ⎝

Tm ,Pb

⎜ c p, Pb(l ) + 2 c p,O2 ( g ) ⎟ dT

⎛ 1 ⎠ ⎞

–200 PbO (

s)

∆∆HH(l(k→→

e)l=) = ∫

∆HT ⎜ c p, Pb(l ) + 2 c p,O2 ( g ) ⎟ dT

Tm ,Pb

Tm ,Pb

⎝ ⎠

–210

–220

d

g

∫

300 500 700 900 1100

∆∆HH(e(l→

→ge))== ∆HTc p, PbO(s ) dT Temperature, K

T (b)

Tm ,Pb

∆H ( g → d ) = ∫

∆H (e → g) = 298

c dT

∫ T

Tm ,Pb

298

p, PbO(s )

c p, PbO ( s ) dT Figure 6.7b (b) The variation, with temperature, of the enthalpies of (Pb + 1/2O 2 ) an

Thus,

∆H ( g → d ) =

∫Tm ,Pb

c p, PbO( s ) dT Table 6.1 Thermochemical Data for Pb, PbO, and O2

HPbo(298) = –219,000 J/K

∆H∆(H

l→( ge)→

= ∆dH)T=

∫ c p, PbO( s ) dT

Thermochemistry

Tm ,Pb Tm ,Pb

∆H (e → g) =

∫ T

c p, PbO(s ) dT

Thus, 298

∆H ( g → d ) =

∫ Tm ,Pb

c p, PbO( s ) dT

⎛ Tm ,Pb

1 ⎞

Thus, ∆HT = ∆H 298 K +

298 ⎝ ∫ c

⎜ p, PbO( s ) − c p, Pb ( s ) − c , O2 ( g ) ⎟ dT

HEATpCAPACITY,

2 ⎠

ENTHALPY, ENTROPY

T

⎛ T ⎛ 1 ⎞ 1 ⎞

∫

∫m298,Pb +⎝ Tm,Pb ⎜⎝ c p,PbO(s) 2− c p,Pb(l⎠) − 2 c p,O2 (g) ⎟⎠ dT 40

m ,Pb

50

∆HT = ∆H−

298∆ +

K H ⎜ c p , PbO ( s ) − c p , Pb ( s ) − c p , O

2 ( g ) ⎟ dT T T’

l

)

⎛ T

1 ⎞ 2(g

= −219, ∫000 +

30 /2O

− ∆H m, Pb + c 6 0 0 − c − c p,O2 ( g ) ⎟ dT + 1

⎜ p, PbO( s ) p, Pb ( l ) Pb

Tm ,Pb ⎝ 2 ⎠ −3 520 −2 k

600 298 j

∫

10 f

Enthalpy, H, kJ

−3 −2

= −219, 000 + (−T 0.7 + 14.96 × 10 T + 0.85 × 10 T )dT 5

a

∫

298 −3 −2 0

− 4810 + (−9.3 + 27.8 × 10 T + 0.85 × 10 T )dT

T

5

∫

–180 e

− 4810 + 3 + 27.8 × 10 −3 T + 0.85 × 10 5 T −2 )dT

(−9.600

600 –190

PbO (

s)

givesΔ H

gives Δ1000

H 1000 = – 216,700

= – 216,700 J at T' J= at T' K,= as

1000 1000 K,inasFigures

is seen is seen6.7binand

Figures

6.8. 6.7b and 6.8. –200

re6.8

re 6.8shows

shows

the the variation

variation of TΔwith

of Δ H PbO, H PbO, with

temperature

T temperature

in the range in

298– the

1100

–210

range

K. d 298– g

1100 K.

–220

ee temperature

temperature of interest is higher

of interest is than

higherthe melting

than the temperatures of both the metal

melting temperatures of

300 both

500 the metal

700 900 1100

its oxide, then both enthalpies of melting must be considered. For example,(b) with Temperature, K

its oxide, then both enthalpies of melting must be considered. For example, with

ence to Figure 6.9, which is drawn for the general oxidation,

ence to Figure 6.9, which is drawn for the general oxidation,

Figure 6.7b (b) The variation, with temperature, of the enthalpies of (Pb + 1/2O ) an 2

1

M + O2 = MO

2 1 Table 6.1 Thermochemical Data for Pb, PbO, and O2

M+ O2 = MO HPbo(298) = –219,000 J/K

600

∫

= −219, 000 +

(−0.7 + 14.96 × 10 T + 0.85 × 10 T )dT −3

5 −2

Thermochemistry

298

–224

T 300 500 700 900 1100

∫ (−of9.3Δ+H27PbO,

shows the−variation T with

T + 0temperature

.85 × 10 T )dT in the range 298– 1100 K.

−3 −2

4810 + .8 × 10 5

Temperature, K

600

erature of interest is higher than the melting temperatures of both the metal

de, then

gives both

Δ H 1000

If enthalpies

= – 216,700

the J at T'of

temperature melting

= of

1000 K, as must

interestis is

seen be

in considered.

Figure 6.8 The and

Figures

higher than6.7b For

variation,

the=melting

1/2O PbO.

example,

6.8. with with of both the metal and its

temperature, of the enthalpy change for the reaction Pb +

temperatures

6.8 shows the variation of Δ H PbO, T with temperature in the range 298– 1100 K.

2

oxide, then isboth

drawn for the general

enthalpies oxidation,

temperature of interest is higher than the meltingoftemperatures

melting must

of bothbe

the considered.

metal

ts oxide, then both enthalpies of melting must be considered. For example, with

1 general oxidation,

ence to Figure 6.9, which is drawn for the

M+ O2 = MO

1 2

M+ O2 = MO

2 O 2(g)

M (l) + 1/2

⎛ Tm ,M

1 ⎞

∫

∆HT = ∆H 298 + T ⎛ ⎜ c p, MO( s ) − c p1, M( s ) −⎞ c p,O2 ( g ) ⎟ dT

∫298 ⎝

m ,M

∆HT = ∆H 298 + 298⎜ c p⎝, MO( s ) − c p, M( s ) − c p,O ( g ) ⎟ 2

2 ⎠

dT ⎠2 DHm,M

DHT

O 2(g )

+ 1/2

c p,⎛MO(s ) − c p, M(l ) − c p,O ( g ) ⎟ dT ⎞

Tm ,T

m ,⎛MO 1 ⎞1

− ∆H m, M +∫T ⎝ ⎜ c p, MO(s ) − c2p, M(l ) −⎠ c p,O2 (0g ) ⎟ dT

M (s)

∫

MO

MO (l)

Enthalpy

− ∆H m, M + ⎜ 2

Tm ,M ⎝ 2 ⎠

m ,M

T

⎛ 1 ⎞

∫

DHm,MO

+ ∆H m, MO + ⎜ c p, MO(l ) − c p, M(l ) − c p,O2 ( g ) ⎟ dT DH298

Tm ,MO ⎝ ⎛ ⎠ 1 ⎞

T 2

+ ∆H m, MO +

∫ Tm ,MO

⎜⎝ c p , MO ( l ) − c p , M(l ) −

2

c p , O 2 ( g ) ⎟⎠ dT MO (s)

Temperature

Adiabatic Flame Temperature

Maximum temperature of the flame that can be achieved theoretically

when fuel is burned

temperature that the flame can achieve

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

make the flame

Adiabatic Flame Temperature

Reactants at T1 burning Products at T2

C + O2 = CO2

2H + 1/2O2 = H2O

CO2 and H2O are the combustion reactions then the products can be

ascertained from the composition of the fuel and amount of air and or

oxygen supplied for its burning

T1

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

298

The temperature rise of the product can thus be calculated from these

knowing the mass of the reactants and the products and the Cp values

for CO, CO2 ,H2O, etc. be known for that temperature range.

Conclusions from 1st law

1. Energy cannot be created nor can it be destroyed, it changes only its form

2. Energy can be interconverted.

3. Although the first law as such does not impose any limitation on such interconversion

and as is observed in practice, that mechanical work can be fully converted to heat energy, yet out

of all conceivable changes, only some actually occur in practice in fully converting the form,

whereas many others do not do so.

4. There is a certain tendency for the conversion of energy to occur in some preferential direction

rather than for either direction to be equally possible.

MM209 - Thermodynamics

Instructor : Aswani Yella

2nd law of thermodynamics

First law → law of conservation of energy → universally accepted as soon as it was

stated → because it appeared reasonable and in accord with human intuition.

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

traditional thought.

Second law together with the first law lays the foundation for the thermodynamic

method of describing the behaviour of matter

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

2. It will move of its own accord to some other state

2nd law of thermodynamics

• If the system is in equilibrium with surroundings, → left to itself, → it will remain the

same.

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

spontaneously move towards equilibrium.

• 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

↓

Inverse does not take place spontaneously

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.

Atmospheric air

Q

at T0and energy are fine concepts that allow us to quantify and predict well

Conservation of mass

many phenomena which are observed in nature. And if a phenomenon can be repeated, it

becomes subject to prediction, and can be thought of as a science.

However, conservation of mass Time

and energy, by themselves,Time

admit as possibilities phenom-

Body at T0 < T < Ti T0

ena which are not observed

Ti > T0 in nature! For instance consider an isolated system composed of

two equal masses of liquid water. See Fig. 7.1. The first is at TA = 310 K, the second is at

(a)

Atmospheric air A B

at p0

Valve T = 320 K T = 280 K

Air at B Air

A

pi > p0 Air at

not observed in nature

p0 < p < pi p0

T = 310 K T = 290 K t ∞

(b) A B

T = 300 K T = 300 K

observed in nature

Body at Time Time

T0 < T < Ti T0

Ti > T0

System B → Air held at high pressure move towards low pressure surrounds when the

valve is opened.

(a)

Atmospheric air

at p0

Valve

Air at Air

pi > p0 Air at

p0 < p < pi p0

(b)

Air held at a higher pressure moves towards lower pressure

(b)

Mass

Mass

zi

0 < z < zi Mass

Mass suspended at an

↓

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.

↓

In each cases, a fuel or electrical input would be required for the device to function so

that a permanent change in surroundings be bought

2nd law of thermodynamics

Not every process that is consistent with energy conservation can occur.

Also energy conservations does not predict the preferred direction and it does not permit the

process that can occur to be distinguished from those that cannot.

1st law does not predict how fast/slow a system reached equilibrium

Eg:- Some chemical reactions → Instantaneously

2nd law of thermodynamics

Some aspect of the world determines the spontaneous direction of change, the

direction that does not require what to bring the change.

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

constant

2. If the energy of the system does decrease during spontaneous then the energy of the

surroundings also should increase by the same amount and just as spontaneous.

Therefore, when change occurs, internal energy of an isolated system remains constant

but it is parcelled out in many ways.

2nd law of thermodynamics

Can it be therefore, that the direction of change is related to distribution of energy?

This idea is the key and that spontaneous changes are always accompanied by

dispersal of energy.

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

(the surroundings)

in which the ball is at rest with all its energy dispersed

into disorderly thermal motion of molecules in the air and

of the atoms of the virtually infinite floor

2nd law of thermodynamics

A ball resting on a warm floor has never been observed to start bouncing

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

localization of energy from the myriad vibrations of

the atoms of the floor into the much smaller number

of atoms that constitute the ball

upwards its atoms must all move in the same

direction. The localization of random, disorderly

motion as concerted, ordered motion is so unlikely

that we can dismiss it as virtually impossible

The reverse has never been observed to take place on a macroscopic scale.

2nd law of thermodynamics

Signpost

96 of 3spontaneous change: we need96to look

THE SECOND LAW

3 THE

for the direction

SECOND LAWof change that

leads to dispersal of the total energy of the isolated system.

is spread out

is spread out as thermal motion of the atoms of the fl

spontaneous

spontaneous because it is highly improbable that

leading to un

leading to uniform motion of the ball’s atoms. A gas d

because to do

because to do so the random motion of its molecules,

tion of kineti

tion of kinetic energy throughout the container, woul

same region

same region of the container, thereby localizing the

spontaneous

spontaneous expansion, is a natural consequence of en

as the gas m

as the gas molecules occupy a larger volume. An o

become warm

become warmer than its surroundings because it is hig

of randomly

(a)of randomly vibrating (b) atoms in the surroundings will

(a) (b) mal motion

mal motion in the object. The opposite change, the s

into the surr

A ballFig.resting Fig.For

into

3.3 the

the

The ball to

molecular fly

surroundings upwards,

as some

thermal

interpretation of of

motion,

the the is natural.

3.3 Theon a warm

molecular surface; the

interpretation of the It may see

atomsirreversibility

are undergoing thermal motionLaw. random

irreversibility

It may vibrational

expressed

seem verybymotion

the

puzzling would

Second

thatLaw. have

the to

spreading out o

expressed by the Second the formatio

(a)change

A ball

the into on

resting

formation coordinated,

a warm

of directed

surface;

such ordered the motion.

structures as crystals o

(a) A ball resting on a warm surface; the course, we sh

atoms are undergoing

course, we shall thermal

see that motion of energy and matt

dispersal

atoms are undergoing thermal motion forms.

(vibration, in this instance), as indicated by

(vibration, in this instance), as indicated by forms.

Such a conversion is highly improbable

the arrows. (b) For the ball to fly upwards,

the arrows. (b) For the ball to fly upwards,

some of the random vibrational motion

some of the random vibrational motion 3.2 Entrop

would have to change into coordinated,

would Entropy

3.2 have to change into coordinated,

2nd law of thermodynamics

A process which involves the spontaneous movement of a system from non-equilibrium

state to an equilibrium state is called a natural/spontaneous/real process .

Such process cannot be reversed naturally less an external source is used → hence

termed “IRREVERSIBLE”

(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

although never occurring in nature, is imaginable.

↓

Such ideal process→ reversible process → Friction, electric resistance or other such

sources of dissipation are eliminated.

2nd law of thermodynamics

Since the degree of irreversibility of a process is path dependent, it should be possible

for the process to be conducted in such a manner that the degree of irreversibility is

minimized.

zero and in which no degradation of energy occurs.

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

reversible process.

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

equilibrium.

A reversible process which takes the system from the state A to the state B is one in

which the process path passes through a continuum of equilibrium states. Such a path

is, of course, an idealization, but it is possible to conduct an actual process in such a

manner that it is virtually reversible.

2nd law of thermodynamics

Such an actual process (sometimes called a quasi-static process) is one which proceeds

under the influence of an infinitesimally small driving force, such that, during the process,

the system is never more than an infinitesimal amount from equilibrium.

If, at any point along the path, the small external influence is removed, then the process

ceases; if the direction of the small external influence is reversed, then the direction of

the process is reversed.

2nd law of thermodynamics

46 Introduction to the Thermodynamics of Materials

Consider a system of water and water vapor at the uniform temperature

3.5 AN ILLUSTRATION T contained

OF IRREVERSIBLE in

AND REVERSIBLE

a cylinder fitted with a frictionless piston, and let the cylinder be placed in thermal

PROCESSES

Consider a system T. at the uniform temperature T contained

of water and water vapor

cylinder fitted with a frictionless piston, and let the cylinder be placed in thermal contact w

heat reservoir which is also at the constant temperature T. This system is shown in Fig

pressure PH2O(T), which is the saturated vapor pressure

of water at the temperature T.

pressure acting on the piston, Pext, equals the internal

pressure acting on the piston,PH2O(T) and when the

temperature of the water+ water vapor in the cylinder

equals the temperature of the constant temperature

heat reservoir Figure 3.2 A thermostalled piston and cylinder containing water and

water vapor.

saturated vapor pressure of water at the temperature T. The system is exactly

equilibrium when the external pressure acting on the piston, Pext, equals the inte

pressure acting on the piston, , and when the temperature of the water+w

!d: \ p A A \__ )A _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 a system of water and water vapor at the uniform temperature T contained

If the external pressure acting on the piston, Pext is suddenly

cylinder fitted with decreased

a frictionless piston, andby

let theacylinder

finite be placed in thermal contact w

amount ΔP, then the imbalance in pressure causes the piston to accelerate rapidly out

heat reservoir which is also at the constant temperature T. This system is shown in Fig

of the cylinder.

decreases the water vapor pressure to a value below its

saturation (and hence equilibrium) value, and thus water

spontaneously evaporates in an attempt to reestablish

equilibrium between the water and its vapor.

water vapor.

The spontaneous evaporation, being endothermic, decreases the temperature of the

water, and hence sets up a temperature gradient between the heat reservoir and the

The water vapor in the cylinder exerts a certain pressure

saturated vapor pressure of water at the temperature T. The system is exactly

, which is

flow spontaneously fromon the

when the external pressure acting heat

the piston, Pext, equals the inte

thermal equilibrium between

pressure acting on the piston,

the two

, and when the temperature of the water+w

in the cylinder equals the temperature T of the constant-temperature heat reserv

If the external pressure acting on the piston, Pext is suddenly decreased by a finite amo

P, then the imbalance in pressure causes the piston to accelerate rapidly out of

!d: \ p A A \__ )A _gA 8 :AA b\dA: ) YA !bgpYA \2 p A A !d

A\QY gJ YAndp\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!__

If, when 1 mole of water has evaporated, the external pressure acting on the piston is

Y!ppAd \d ! Q\Ad

Consider a system of water and water vapor at the uniform temperature T contained

instantaneously increased to the original value, P , then evaporation of the water

cylinder fitted with a frictionless piston, and let the cylinder be placed in thermal contact w

ext

heat reservoir which is also at the constant temperature T. This system is shown in Fig

vapor ceases, the flow of heat ceases, and compete equilibrium is reestablished.

process equals (Pext– ΔP)V, where V is the

molar volume of

water vapor at .

suddenly increased by a finite amount ΔP, then the

piston accelerates rapidly into the piston

If, when 1 mole of water vapor has been condensed, Figure the external pressure

3.2 A thermostalled acting

piston and cylinder on water and

containing

water vapor.

the piston is instantaneously decreased to its original value, equilibrium is reestablished

, which is

and the work done on the system equals (Pext+ ΔP)V The water vapor in the cylinder exerts a certain pressure

saturated vapor pressure of water at the temperature T. The system is exactly

equilibrium when the external pressure acting on the piston, Pext, equals the inte

pressure acting on the piston, , and when the temperature of the water+w

The permanent change in the external agency caused by the cyclic process is thus 2ΔPV.

vapor in the cylinder equals the temperature T of the constant-temperature heat reserv

If the external pressure acting on the piston, Pext is suddenly decreased by a finite amo

P, then the imbalance in pressure causes the piston to accelerate rapidly out of

!d: \ p
A
A \__ )A _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.

slower the process, the smaller the degree

of undersaturation of the water vapor, and

the smaller the temperature gradient.

greater the opportunity afforded to the evaporation and

heat flow process to “keep up” with equilibrium

u YA p A A \dFigure YA3.2Q! \d YA p\gd r!s \ :AA b\dA:

A thermostalled piston and cylinder containing water and

pg:A \d YA p!du J YA ! \ AbgA: water vapor. YA Q! Ap!d: ::Ad_ !d:

Ap!d:

water vapor _g_8

in the cylinder) Abg\dQ

exerts gdA p! \2_A

a certain pressure , which isg

saturated vapor pressure of water at the temperature T. The system is exactly

YA p g2A \ AA \)_A r2su equilibrium when the external pressure acting on the piston, P , equals the inte

ext

pressure acting on the piston, , and when the temperature of the water+w

vapor in the cylinder equals the temperature T of the constant-temperature heat reserv

If the external pressure acting on the piston, Pext is suddenly decreased by a finite amo

P, then the imbalance in pressure causes the piston to accelerate rapidly out of

!d: \ p A A \__ )A _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!__

If, after the evaporation of 1 mole of water, the external pressure is instantaneously

Y!ppAd \d ! Q\Ad

Consider a system of water and water vapor at the uniform temperature T contained

increased to its original value Pext, then the work done by the system equals (P – δP)V.

cylinder fitted with a frictionless piston, and let the cylinder be placed in thermal contact w

heat reservoir which is also at the constant temperatureext T. This system is shown in Fig

increased by P, then work (Pext+ δP)V, is done on the

system to condense 1 mole of

water vapor, and the permanent change in the external

agency equals the work done on the system minus the

work done by the system during the cyclic process

The smaller the value of δP, then the more nearly equal

are the two work terms, and in the limit that they are

equal, no permanent change 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:

Ap!d:

water vapor _g_8

in the cylinder) Abg\dQ

exerts gdA p! \2_A

a certain pressure , which isg

saturated vapor pressure of water at the temperature T. The system is exactly

YA p g2A \ AA \)_A r2su equilibrium when the external pressure acting on the piston, Pext, equals the inte

pressure acting on the piston, , and when the temperature of the water+w

vapor in the cylinder equals the temperature T of the constant-temperature heat reserv

Complete reversibility is approached, only when the process becomes infinitely slow.

If the external pressure acting on the piston, Pext is suddenly decreased by a finite amo

P, then the imbalance in pressure causes the piston to accelerate rapidly out of

2nd law of thermodynamics

ENTROPY AND THE QUANTIFICATION OF IRREVERSIBILITY

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

energy of the system undergoing the process is

degraded

degradation can differ from one process to another

degree of irreversibility, exists

2nd law of thermodynamics

Consider the weight–heat reservoir system

This system consists of a weight–pulley arrangement which is

coupled to a constant-temperature heat reservoir.

60 INTRODUCTION TO THE THERMODYNAMICS OF MATERIALS, S

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

weight.

the weight spontaneously falls, performing work, which is

converted, by means of a suitable system of paddle wheels,

into thermal energy, which enters the constant-temperature

heat reservoir.

Figure 3.1 A weight– pulley– heat reservoir arrangement in which the work do

weight is degraded to thermal energy, which appears in the heat r

acting on the

and Randall * considered the following three processes:

1. The thatreservoir in the weight– heat reservoir system is at the tempera

mechanical energy is converted to thermal energy. weight is allowed to fall, performing work, w, and the thermal energy p

enters the heat reservoir.

2. The heat reservoir at the temperature T 2 is placed in thermal contact w

2nd law of thermodynamics

Now consider the following three60processes:

INTRODUCTION TO THE THERMODYNAMICS OF MATERIALS, S

system is at the temperature T2. The weight is

allowed to fall, performing work, w, and the W

thermal energy produced, q, enters the heat Temperature T2

reservoir.

Figure 3.1 A weight– pulley– heat reservoir arrangement in which the work do

weight is degraded to thermal energy, which appears in the heat

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

T2 is placed in thermal contact with

another heat reservoir at a lower

temperature T1, and the same thermal

W energy, q, is allowed to be transferred

Temperature T2 Temperature T1 from the reservoir at T2 to the reservoir

at T1.

0A weight–

INTRODUCTION TO THE

pulley– heat reservoir THERMODYNAMICS

arrangement in which the OF MATERIALS,

work SIXTH EDITION

done by the falling

T <T1

weight is degraded to thermal energy, which appears 2in the heat reservoir.

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.

ngure

occurs in each of them. However, since process 3 is the sum of processes

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

e degradation occurring in process 3 must be greater than the degrada-

INTRODUCTION TO THE THERMODYNAMICS

60 OF MATERIALS,

INTRODUCTION

2nd law of thermodynamics

SIXTH EDITION

TO THE THERMODYNAMICS OF MATERIALS, SIXTH EDITION

60 INTRODUCTION TO THE THERMODYNAMICS OF MATERIALS, SIXTH E

W

W W Temperature T1

Temperature T2 Temperature T2 Temperature T1

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

weight is degraded to thermal energy, which appears in the heat reservoi

1 Figure

A weight– pulley– heat reservoir arrangement 3.1 Athe

in which weight–

workpulley–

done heat reservoir

by the fallingarrangement in which the work done by the falling

Each of these processes is spontaneous and hence irreversible, and therefore,

weight is degraded to thermal energy, which appearsweight

in theisheat

degraded to thermal energy, which appears in the heat reservoir.

reservoir.

Lewis and Randall* considered the following three processes:

d Randall*

degradation occurs

considered the following three Lewis

processes:

in each of them

and Randall considered the following three processes:

*

1. The heat reservoir in the weight– heat reservoir system is at the temperature T . 2

weight is allowed to fall, performing work, w , and the thermal energy produce

1. The

e heat reservoir in the weight– heat reservoir system heat

is at thereservoir in the weight–

temperature enters the heat reservoir.

T 2 . Theheat reservoir system is at the temperature T 2 . The

ight is allowed to fall, performing work, w , and the thermal energy produced, q , work, w , and the thermal energy produced, q ,

weight is allowed to fall, performing 2. The heat reservoir at the temperature T 2 is placed in thermal contact with ano

enters the heat reservoir. heat reservoir at a lower temperature T 1 , and the same thermal energy, q , is allo

Thermal energy transferred in all three cases is q

ers the heat reservoir.

e heat reservoir at the temperature T 2 is placed 2.in The heat reservoir

thermal contact atwiththe another

to be transferred from the reservoir at T 2 to the reservoir at T 1 .

temperature T 2 is placed in thermal contact with another

3. The heat reservoir in the weight– heat reservoir system is at the temperature T 1 .

Only difference is the temperature of the constant reservoir bath

at reservoir at a lower temperature T 1 , and the sameheat reservoir

thermal at a lower

energy,

to beattransferred

be transferred from the reservoir at T 2 to the reservoir T1.

q , istemperature

allowed T 1 , and the same thermal energy, q , is allowed

from the reservoir at T 2 to the reservoir at T 1 .

weight is allowed to fall, performing work, w , and the thermal energy produce

enters the reservoir.

3. The

e heat reservoir in the weight– heat reservoir system heat

is at thereservoir in the weight–

temperature T 1 . Theheat reservoir system is at the temperature T 1 . The

ight is allowed to fall, performing work, w , and theweight

thermal is allowed

energytoproduced,

fall, performing

q , work, w , and the thermal energy produced, q , Each of these processes is spontaneous and hence irreversible , and the

enters the reservoir.

process 3 can be considered as the sum of processes 1 and 2

ers the reservoir. degradation occurs in each of them. However, since process 3 is the sum of pro

1 and 2, the degradation occurring in process 3 must be greater than the de

of these processes is spontaneous and hence Each irreversible

of these processes

, and istherefore,

spontaneous and hence irreversible , and therefore, tion occurring in each of the processes 1 and 2. Thus, it can be said that pro

degradation occurs in

ion occurs in each of them. However, since process 3 is the sum of processes each of them. However, since process 3 is the sum of processes

is more irreversible than either process 1 or process 2. An examination of th

the degradation occurring in process 3 1must and 2,bethegreater

degradation

than occurring

the degrada- in process 3 must be greater than the degrada- processes indicates that both the amount of thermal energy transferred, q , a

temperatures between which this energy is transferred are important in defi

Degradation or dissipation of energy in the process 3 is higher compared to the

urring in each of the processes 1 and 2. tion

irreversible than either process 1 or process

occurring

Thus,

is more

2. An

it can be in each

irreversible

saidofthat

examination

the process

than either

processes31 and 2. Thus, it can be said that process

of the process

three1 or process 2. An examination of the three

3

quantitative scale of irreversibility. In the case of comparison between proces

degradation occurring in each of the processes 1 and 2

s indicates that both the amount of thermal processes

energy indicates that bothqthe

transferred, , and amount

the of thermal energy transferred, q , and with

process 3, the quantity q / T2 is smaller than the quantity q / T1 , which is in agre

the

the conclusion that process 1 is less irreversible than process 3. The q

temperatures between

tures between which this energy is transferred are important in defining a which this energy is transferred are important in defining q /aT can thus be taken as a measure of the degree of irreversibility of the p

tive scale of irreversibility. In the case of quantitative

comparison scale of irreversibility.

between process 1Inand the case of comparison between process 1 and and the value of q / T is the increase in entropy occurring as a result of th

INTRODUCTION TO THE THERMODYNAMICS

60 OF MATERIALS,

INTRODUCTION

2nd law of thermodynamics

SIXTH EDITION

TO THE THERMODYNAMICS OF MATERIALS, SIXTH EDITION

60 INTRODUCTION TO THE THERMODYNAMICS OF MATERIALS, SIXTH E

W

W W Temperature T1

Temperature T2 Temperature T2 Temperature T1

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

weight is degraded to thermal energy, which appears in the heat reservoi

1 Figure

A weight– pulley– heat reservoir arrangement 3.1 Athe

in which weight–

workpulley–

done heat reservoir

by the fallingarrangement in which the work done by the falling

Process 3 is said to be more irreversible or more spontaneous than either process1 or

weight is degraded to thermal energy, which appearsweight

in theisheat

degraded to thermal energy, which appears in the heat reservoir.

reservoir.

Lewis and Randall* considered the following three processes:

process 2

d Randall* considered the following three Lewis and Randall* considered the following three processes:

processes: 1. The heat reservoir in the weight– heat reservoir system is at the temperature T 2 .

weight is allowed to fall, performing work, w , and the thermal energy produce

1. The

e heat reservoir in the weight– heat reservoir system heat

is at thereservoir in the weight–

temperature enters the heat reservoir.

T 2 . Theheat reservoir system is at the temperature T 2 . The

ight is allowed to fall, performing work, w , and the thermal energy produced, q , work, w , and the thermal energy produced, q ,

weight is allowed to fall, performing 2. The heat reservoir at the temperature T 2 is placed in thermal contact with ano

An examination of the three processes indicates that both the amount of thermal

ers the heat reservoir. enters the heat reservoir. heat reservoir at a lower temperature T 1 , and the same thermal energy, q , is allo

to be transferred from the reservoir at T 2 to the reservoir at T 1 .

e heat reservoir at the temperature T 2 is placed 2.in The heat reservoir

thermal contact atwiththe another

temperature T 2 is placed in thermal contact with another

energy transferred, q, and the temperatures between which this energy is transferred

at reservoir at a lower temperature T 1 , and the sameheat reservoir

thermal at a lower

energy, q , istemperature

3. The heat reservoir in the weight– heat reservoir system is at the temperature T 1 .

allowed T 1 , and the same thermal energy, q , is allowed

weight is allowed to fall, performing work, w , and the thermal energy produce

to beattransferred

be transferred from the reservoir at T 2 to the reservoir T1. from the reservoir at T 2 to the reservoir at T 1 .

are important in defining a quantitative scale of irreversibility

3. The

e heat reservoir in the weight– heat reservoir system heat

is at thereservoir in the weight–

temperature

enters the reservoir.

T 1 . Theheat reservoir system is at the temperature T 1 . The

ight is allowed to fall, performing work, w , and theweight

thermal is allowed

energytoproduced,

fall, performing

q , work, w , and the thermal energy produced, q , Each of these processes is spontaneous and hence irreversible , and the

ers the reservoir. enters the reservoir. degradation occurs in each of them. However, since process 3 is the sum of pro

By comparing process 1 and process 3 we can say that, the quantity q /T2 is smaller

of these processes is spontaneous and hence Each irreversible

of these processes

, and istherefore,

spontaneous and hence irreversible , and therefore,

1 and 2, the degradation occurring in process 3 must be greater than the de

tion occurring in each of the processes 1 and 2. Thus, it can be said that pro

than the quantity q /T1 degradation occurs in

ion occurs in each of them. However, since process 3 is the sum of processes each of them. However, since process 3 is the sum of processes

is more irreversible than either process 1 or process 2. An examination of th

the degradation occurring in process 3 1must and 2,bethegreater

degradation

than occurring

the degrada- in process 3 must be greater than the degrada- processes indicates that both the amount of thermal energy transferred, q , a

temperatures between which this energy is transferred are important in defi

urring in each of the processes 1 and 2. tion occurring

Thus, it can be in each

saidofthat the process

processes31 and 2. Thus, it can be said that process 3

is more irreversible than either process quantitative scale of irreversibility. In the case of comparison between proces

irreversible than either process 1 or process 2. An examination of the three1 or process 2. An examination of the three

process 3, the quantity q / T2 is smaller than the quantity q / T1 , which is in agre

This is in agreement with the conclusion that process 1 is less irreversible than process 3.

s indicates that both the amount of thermal processes

energy indicates that bothqthe

transferred, , and amount

the of thermal energy transferred, q , and with the

the conclusion that process 1 is less irreversible than process 3. The q

temperatures between

tures between which this energy is transferred are important in defining a which this energy is transferred are important in defining q /aT can thus be taken as a measure of the degree of irreversibility of the p

tive scale of irreversibility. In the case of quantitative

comparison scale of irreversibility.

between process 1Inand the case of comparison between process 1 and and the value of q / T is the increase in entropy occurring as a result of th

INTRODUCTION TO THE THERMODYNAMICS

60 OF MATERIALS,

INTRODUCTION

2nd law of thermodynamics

SIXTH EDITION

TO THE THERMODYNAMICS OF MATERIALS, SIXTH EDITION

60 INTRODUCTION TO THE THERMODYNAMICS OF MATERIALS, SIXTH E

W

W W Temperature T1

Temperature T2 Temperature T2 Temperature T1

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

1 The quantity q/T can thus be taken as a measure of the degree of irreversibility of the

Figure

A weight– pulley– heat reservoir arrangement 3.1 Athe

in which weight–

workpulley–

done heat reservoir

by the fallingarrangement in which the work done by the falling

weight is degraded to thermal energy, which appears in the heat reservoi

in theisheat

degraded to thermal energy, which appears in the heat reservoir.

reservoir.

process, and the value of q/T is the increase in entropy occurring as a result of the Lewis and Randall* considered the following three processes:

d Randall* process.

considered the following three Lewis and Randall considered the following three processes:

processes: *

1. The heat reservoir in the weight– heat reservoir system is at the temperature T . 2

weight is allowed to fall, performing work, w , and the thermal energy produce

1. The

e heat reservoir in the weight– heat reservoir system heat

is at thereservoir in the weight–

temperature enters the heat reservoir.

T 2 . Theheat reservoir system is at the temperature T 2 . The

ight is allowed to fall, performing work, w , and the thermal energy produced, q , work, w , and the thermal energy produced, q ,

weight is allowed to fall, performing 2. The heat reservoir at the temperature T 2 is placed in thermal contact with ano

enters the heat reservoir. heat reservoir at a lower temperature T 1 , and the same thermal energy, q , is allo

ers the heat reservoir.

Thus, when the weight–heat reservoir system undergoes a spontaneous process which

e heat reservoir at the temperature T 2 is placed 2.in The heat reservoir

thermal contact atwiththe another

to be transferred from the reservoir at T 2 to the reservoir at T 1 .

temperature T 2 is placed in thermal contact with another

3. The heat reservoir in the weight– heat reservoir system is at the temperature T 1 .

at reservoir at a lower temperature T 1 , and the sameheat reservoir

thermal at a lower

energy, q , istemperature

allowed T 1 , and the same thermal energy, q , is allowed

weight is allowed to fall, performing work, w , and the thermal energy produce

causes the absorption of thermal energy q at the constant temperature T, we can

to beattransferred

be transferred from the reservoir at T 2 to the reservoir T1. from the reservoir at T 2 to the reservoir at T 1 . enters the reservoir.

3. The

e heat reservoir in the weight– heat reservoir system heat

is at thereservoir in the weight–

temperature T 1 . Theheat reservoir system is at the temperature T 1 . The

define a quantity produced by the system, lets say for now denoted as ΔS is given by

ight is allowed to fall, performing work, w , and theweight

thermal is allowed

energytoproduced,

fall, performing

q , work, w , and the thermal energy produced, q , Each of these processes is spontaneous and hence irreversible , and the

ers the reservoir. enters the reservoir. degradation occurs in each of them. However, since process 3 is the sum of pro

ΔS=q/T 1 and 2, the degradation occurring in process 3 must be greater than the de

of these processes is spontaneous and hence Each irreversible

of these processes

, and istherefore,

spontaneous and hence irreversible , and therefore, tion occurring in each of the processes 1 and 2. Thus, it can be said that pro

degradation occurs in

ion occurs in each of them. However, since process 3 is the sum of processes each of them. However, since process 3 is the sum of processes

is more irreversible than either process 1 or process 2. An examination of th

This value is larger in the case of the lower-temperature reservoir. The increase in the

the degradation occurring in process 3 1must and 2,bethegreater

degradation

than occurring

the degrada- in process 3 must be greater than the degrada- processes indicates that both the amount of thermal energy transferred, q , a

temperatures between which this energy is transferred are important in defi

urring in each of the processes 1 and 2. tion occurring

Thus, it can be in each

saidofthat the process

processes31 and 2. Thus, it can be said that process 3

quantity q/T caused by the process is thus a measure of the degree of irreversibility of

irreversible than either process 1 or process is more

2. An irreversible

examinationthan either

of the process

three1 or process 2. An examination of the three

quantitative scale of irreversibility. In the case of comparison between proces

process 3, the quantity q / T2 is smaller than the quantity q / T1 , which is in agre

the process.

s indicates that both the amount of thermal processes

energy

temperatures

indicates

between

that bothqthe

transferred,

which

, and

this

amount

the of thermal energy transferred, q , and with

energy is transferred are important in defining

the

the conclusion that process 1 is less irreversible than process 3. The q

tures between which this energy is transferred are important in defining a q /aT can thus be taken as a measure of the degree of irreversibility of the p

tive scale of irreversibility. In the case of quantitative

comparison scale of irreversibility.

between process 1Inand the case of comparison between process 1 and and the value of q / T is the increase in entropy occurring as a result of th

43

2nd law of thermodynamics

MATHEMATICAL INTERLUDE III: PFAFFIAN DIFFERENTIAL FORMS

Note: It is obvious that two (reversible) adiabats cannot intersect. Once Carathéo-

dory’s Principle is accepted, the concept of entropy can be defined without recourse

toCaratheodary formulation of 2 law

nd

Carnot cycles by using mathematical properties of certain linear differential

equations called Pfaffian expressions, summarized in the following mathematical

interlude.

Avoids the use of cycles and heat engines

MATHEMATICAL INTERLUDE III: PFAFFIAN DIFFERENTIAL FORMS 43

Uses mathematical terms and axioms to develop 2nd law of thermodynamics

4.6

Note: MATHEMATICAL

It is obvious that two INTERLUDE III: PFAFFIAN

(reversible) adiabats cannot intersect. Once Carathéo-

DIFFERENTIAL

dory’s Principle isFORMS

accepted, the concept of entropy can be defined without recourse

to Carnot cycles by using mathematical properties of certain linear differential

Caratheodary

A differential

equations called Theorem

expression

Pfaffian of the form summarized in the following mathematical

expressions,

Ifinterlude.

a Pfaffian expression

dL ¼ !i Xi dxi ð4-24Þ

has the property for which, in the neighborhood of any point P, there are points that

where Xi isbea connected

4.6cannot function oftoINTERLUDE

MATHEMATICAL the variables

P along xIII:

curves 2 ; . . satisfy

1 , xthat

PFAFFIAN. ; xr , isthe

called a Pfaffian

equation dL = 0, then the

differential

Pfaffian form.

DIFFERENTIAL The

expression equation

FORMShas an integrating factor

dL ¼ !i Xi dxi ¼ 0 ð4-25Þ

A differential expression

A differential of theofform

expression the form

is called Pfaffian differential equation. The differential forms are sometimes

dL ¼ ! X dx ð4-24Þ

exact, although generally they are not.i i i

We consider

where X is a three special

function of cases.

the variables x2 ; x2,…xn,

x1 ,x1, . . . ; xr , isiscalled

where Xi is a function of the

i variables calledaaPfaffian

Pfaffian differential form

differential form. The equation

1) dL is exact. Then

4.6 MATHEMATICAL INTERLUDE III: PFAFFIAN

nd

DIFFERENTIAL FORMS 2 law of thermodynamics

A differential expression of the form

If a Pfaffian expression

dL ¼ !i Xi dxi ð4-24Þ

has the property for which, in the neighborhood of any point P, there are points that

where Xi isbea connected

cannot function oftothe variables

P along curves 2 ; . . satisfy

x1 , xthat . ; xr , isthe

called a Pfaffian

equation dL = 0, then the

differential form. The equation

Pfaffian expression has an integrating factor

dL ¼ !i Xi dxi ¼ 0 ð4-25Þ

From the Caratheodary theorem the following conclusions can be drawn

is called Pfaffian differential equation. The differential forms are sometimes

exact, although

(a) the generally

existence of anthey are not. denominator for the differential expression for a

integrating

We considerheat

reversible three specialthat

transfer cases.

transformed the inexact differential into an exact

differential, and thereby providing an operational definition for some state function

1) dL is exact. Then

(b) the general tendency of this state function to increase.

qXi =qxj ¼ qXj qxi for all i; j ¼ 1; 2; . . . ; r ð4-26Þ

This conclusion, which is another way of stating the Second Law, is known as the

An integrating

Caratheodory factor, "(x

principle. 1 , . .be

It can . ,xrstated

), is a as

factor that turns the inexact

differential

In the dL intoofanevery

neighborhood exactequilibrium

one, which statewe represent as ds. Writingsystem, there exist

of a thermodynamic

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

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

some examples involving only two variables. These do not provide the

generality we must have to treat thermodynamic systems of three or more

<.,-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

R:D

.~ .

⎜ ⎟

"~

⎝ ⎠Vm R

~

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

~1 ~

Vm

..a

~

~

4.6 MATHEMATICAL INTERLUDE III: PFAFFIAN

DIFFERENTIAL FORMS

2nd law of thermodynamics

A differential expression of the form

If a Pfaffian expression

dL ¼ !i Xi dxi ð4-24Þ

has the property for which, in the neighborhood of any point P, there are points that

where Xi isbea connected

cannot function oftothe variables

P along curves 2 ; . . satisfy

x1 , xthat . ; xr , isthe

called a Pfaffian

equation dL = 0, then the

differential

Pfaffian form. The equation

expression has an integrating factor

dL ¼ !i Xi dxi ¼ 0 ð4-25Þ

Mathematically, it can be shown that a two-dimensional Pfaffian is either exact, or, if it is

is called

inexact,Pfaffian differential

an integrating equation. The

denominator candifferential

always beforms aretosometimes

found convert it into a new, exact,

exact, although generally they are not.

differential.

We consider three special cases.

1) dL is exact. Then

Caratheodory showed that expressions for dqrev fall into the class of inexact but

integrable differential

qXi =qxj ¼expressions.

qXj qxi for That all i; jis,¼an integrating

1; 2; ...;r denominator

ð4-26Þ exists that can

convert the inexact differential into an exact differential.

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

An integrating factor, "(x1 , . . . ,xr ), is a factor that turns the inexact

differential dL into an exact one, which we represent as ds. Writing

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).

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

From a given thermodynamic state of the system, there are states that cannot be

reached from the initial state by way of any adiabatic process.

2nd law of thermodynamics

Let us define the system as being characterized by an empirical temperature, θ and any

other number of variables, x1,x2, ….xn

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

temperature T, and the other variable,

xj, will be the analogue of pressure p.

isotherms

2nd law of thermodynamics

Lets take two isotherms, θ1 and θ2, with θ2 < θ1

Lets take State 1, which is defined by θ1 and x1, can be connected to states 1' and 1"

by a series of reversible isothermal processes The First and Second Laws of Thermodynamics 69

isothermal path, and we will assume that this flow

of heat is a continuous function of x1 along the

isotherms, with the absorption or liberation

depending upon the direction in which x1 is varied.

Lets say heat is liberated in going from 1 to 1', then increasing amount of heat is

liberated on going from 1 to states farther and farther removed from 1 such as 1".

If the direction of the process is switched and the system proceeds from 1" to

1' or on to 1, heat would be absorbed in increasing amounts.

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

2nd law of thermodynamics

For each state identified on the θ1 isothermal as 1, 1', 1".... , let us draw paths

representing reversible adiabatic processes that intersect a second isotherm

at θ2. The First and Second Laws of Thermodynamics 69

from states 1, 1' and 1" on θ1 with those on θ2 are

denoted by 2, 2' and 2", respectively.

Along the three paths, 1-2, 1'-2', and 1"-2", no heat is absorbed or liberated because

the processes that connect these points are defined to be adiabatic.

We wish to show that no points to the left of 2 on the isotherm θ2 are accessible from

point 1 via any adiabatic path, reversible orFigure

irreversible.

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

pressure. (a) Reversible adiabatic paths (solid lines: 1 " ~ 2 " ; 1' ~ 2 ' ; and 1 ~ 2 )

connect states on two isothermal lines of a general thermodynamic system: An

irreversible adiabatic path (dotted line: 1 --~ 2') can be shown to be forbidden, while an

2nd law of thermodynamics

Suppose we assume that some adiabatic path does exist between 1 and 2'.

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

that arising from the last step 1’ - 1

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

Thus, for this process, w is negative (and therefore performed by the system), since q1’-1

is positive, having been absorbed from the reservoir.

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

pressure. (a) Reversible adiabatic paths (solid lines: 1 " ~ 2 " ; 1' ~ 2 ' ; and 1 ~ 2 )

connect states on two isothermal lines of a general thermodynamic system: An

irreversible adiabatic path (dotted line: 1 --~ 2') can be shown to be forbidden, while an

2nd law of thermodynamics

Thus, for this process, w is negative (and therefore performed by the system), since q1’-1

is positive, having been absorbed from the reservoir.

The First and Second Laws of Thermodynamics 69

completely convert heat absorbed at a high

temperature reservoir into work.

possible

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

path.

pressure. (a) Reversible adiabatic paths (solid lines: 1 " ~ 2 " ; 1' ~ 2 ' ; and 1 ~ 2 )

connect states on two isothermal lines of a general thermodynamic system: An

irreversible adiabatic path (dotted line: 1 --~ 2') can be shown to be forbidden, while an

2nd law of thermodynamics

What about points to the right of 2? Can they be reached?

Consider an adiabatic path from point 1 to point 2a that is also located onandthe

The First isothermal

Second Laws of Thermodynamics 69

θ2.

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

heat.

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

thermodynamics.

Thus, there are states to the right of 2 on the isotherm θ2of that

Figure 2.11 Graph are

empirical accessible

temperature from

0 against x, a state variable such as

pressure. (a) Reversible adiabatic paths (solid lines: 1 " ~ 2 " ; 1' ~ 2 ' ; and 1 ~ 2 )

1 via an adiabatic path. connect states on two isothermal lines of a general thermodynamic system: An

irreversible adiabatic path (dotted line: 1 --~ 2') can be shown to be forbidden, while an

2nd law of thermodynamics

Since the only constraint we have placed on θ2 is that it be less than θ1, the

second isotherm can be as arbitrarily close to the first as we wish.

There are states located in the plane defined by θ and x1 that are inaccessible from

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

state 1. (a) Reversible adiabatic paths (solid lines: 1 " ~ 2 " ; 1' ~ 2 ' ; and 1 ~ 2 )

pressure.

connect states on two isothermal lines of a general thermodynamic system: An

irreversible adiabatic path (dotted line: 1 --~ 2') can be shown to be forbidden, while an

There is aadiabatic

irreversible sense of pathdirection to the

(dashed line: 1 ~ location of the

2a) is allowed. (b) inaccessible states.

A reversible adiabatic

path through state 1 at temperature 01 divides the states at lower temperatures into two

State 2, the

regions, thosestate reached

that are accessiblefrom 1 by a reversible

via irreversible adiabatic

adiabatic paths and those path,

that arerepresents

the division

not.

between the states on the second isotherm that are accessible and inaccessible from

state

heat 1.

is liberated in going from 1 to 1', then increasing a m o u n t s of heat are

same state 1 as earlier. The value of x2 in state 1 will fix the location of this state

on the isotherm in the new direction. A reversible adiabatic path can be

2nd law of thermodynamics

constructed that connects state 1 with a state on the second isothermal in the x2

direction. Irreversible states located on one side of this point will be inaccessible

from state

Within the neighborhood 1 by adiabatic

of every paths,

state in this while states located

thermodynamic system,onthere

the are

otherstates

side of that

point will

that cannot be reached be accessible.

via adiabatic Thus, there exist states located on the plane defined by 0

paths.

and x2 that are inaccessible from point 1. Similar conclusions can be drawn by

considering isotherms localized on the planes formed by 0 and each of the xi.

Thus, we can conclude that, within the neighborhood of every state in this

Given the existence of these states, then, the existence of an integrating denominator

thermodynamic system, there are states that cannot be reached via adiabatic

for the differential element of reversible heat, dqrev, is guaranteed from Caratheodory's

paths. Given the existence of these states, then, the existence of an integrating

theorem.

denominator for the differential element of reversible heat, ~Sqrev, is guaranteed

from Carath6odory's

66 Chemical theorem.

Thermodynamics: PrinciplesOur next task is to identify this integrating

and Applications

denominator.

dqrev for an ideal gas undergoing only pressure-volume work is an inexact differential.

so that

2.2f The Identification of the Absolute (Ideal Gas) Temperature

RT

as(Sqrev

the-- Integrating

d Vm + Denominator

dT. (2.43)

We have previously Vm showna Tthat "mthe Pfaff differential ~Sq~v for an ideal gas

undergoing only pressure-volume work {equation (2.43)} is an inexact

Applying the

differential. It condition

is easy toforshow

exactness

that gives"

division of equation (2.43) by the absolute

We can easily show that division

temperature of above

T yields equation

an exact by the expression.

differential absolute temperature

The divisionT gives

yields an exact differential expression.

qrev R R

= ~ d Vm + - d T. (2.45)

T OTVm VmT aT

undergoing only pressure-volume work {equation (2.43)} is an inexact

differential. It is easy to show that division of equation (2.43) by the absolute

2nd law of thermodynamics

temperature T yields an exact differential expression. The division gives

qrev R

= ~ d Vm + - d T. (2.45)

T Vm T aT

Application of the for exactness

condition for shows thatshows

exactness both derivatives equal zeroequal

that both derivatives

zero, so equation (2.45) must be exact. Thus, we have determined that when an

ideal⎛⎜ ∂gas

⎛ R ⎞is⎞ involved, T is an integrating denominator for ~Sqrev, and the right

⎜ ⎟⎟ ⎛ 1 ⎞⎛ ∂ ⎛ ∂U m ⎞ ⎞ ⎛ 1 ⎞⎛ ∂ ⎛ ∂U m ⎞ ⎞

hand⎜ side⎝ Vm ⎠ of

⎟ equation (2.45) ⎜is ⎟the

⎜ total

⎜ ⎟differential

⎟ = ⎜ ⎟⎜⎜ for ⎜ a⎟ state

⎟⎟ = 0function that we

=0 ⎝ T ⎠ ∂V

⎝ m ⎝ ∂T ⎠ ⎝ T ⎠ ∂T ∂V

⎜ ∂T ⎟ Vm ⎠T ⎝ ⎝ m ⎠T ⎠Vm

will represent as dS. cc

⎜ ⎟

What

⎝ we

⎠Vm must consider now is the generality of the result obtained for the

special case of the ideal gas. We define a new thermodynamic system that is the

When an ideal gas is involved, T is an integrating denominator for dqrev

cc We should remember that an integrating denominator for all inexact differential expressions in

two dimensions is guaranteed. Hence, its existence for the differential reversible heat element is

not unexpected.

Caratheodary has indeed shown that absolute temperature functions equally well as an

integrating factor not only the ideal gas but for the most complex systems also

2nd law of thermodynamics

The Caratheodory treatment is grounded in the mathematical behavior of Pfaffian

differential expressions, and the observation that a differential element of heat for a

reversible process can be written in this form, where the dxi's represent state variables.

It is not generally possible to write such expressions for the differential element of heat

for irreversible processes, and therefore, an integrating denominator does not exist for

irreversible processes.

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

to reversible processes.

process would not yield an entropy change for the process.

Entropy is a state function, the changes associated with irreversible processes can still

be calculated if a reversible path, perhaps a purely hypothetical one, can be conceived

for which dqrev/T can be evaluated.

2nd law of thermodynamics

For reversible processes, dqrev is an inexact Pfaffian differential expression, and dS

is an exact one

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

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

is satisfied

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

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

the entropy surface, S2

Figure entropy.

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

curve marked (Sqrev = 0 represents a reversible adiabatic path that connects two

that lie on the entropy surface, $2. The dashed curves marked ~Sqirr = 0 are irrev

paths that connect states on different entropy surfaces. Only one of these two pa

be allowed; the other will be forbidden.

dS = 0 for a reversible adiabatic process because dqrev = 0.

it is easy to see that dS = 0 for a reversible adiabatic process because ~ q r e

Two points which can be connected by a reversible adiabatic path must

Two points which can be connected by a reversible adiabatic path must lie on the same

the same entropy surface and a solution curve must lie wholly within a s

surface.

entropy surface and a solution curve must lie wholly within a solution surface.

The solution surfaces cannot intersect. If they did, states located

points of intersection would have multiple values of entropy, and this

violate a fundamental property of state functions. Thus, the surfaces

expected to be ordered monotonically, either systematically increasi

All points on the same surface can be connected by some solution curve (reversible

decreasing) as one proceeds in a given direction from surface to surface. F

adiabatic process). purposes, let us assume Sl > $2 > $3 in Figure 2.12.

Presumably all points on the same surface can be connected by

solution curve (reversible adiabatic process). However, states on surface

example, cannot be connected to states on either S~ or $3 by any rev

2nd law of thermodynamics

All points on the same surface can be connected by some solution curve (reversible

adiabatic process).

The First and Second Laws of Thermodynam

1 i

States on surface S2, cannot be connected to states on The First and Second Laws of Thermodynamics

r:v I

69

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

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

Sl >

We have shown previously that for any given initial state there are states that are

curve marked (Sqrev = 0 represents a reversible adiabatic path that connects two

that lie on the entropy surface, $2. The dashed curves marked ~Sqirr = 0 are irrev

accessible via adiabatic paths from the initial state, as well as states that are

paths that connect states on different entropy surfaces. Only one of these two pa

be allowed; the other will be forbidden.

inaccessible from that initial state by way of adiabatic paths.

it is easy to see that dS = 0 for a reversible adiabatic process because ~ q r e

Two points which can be connected by a reversible adiabatic path must

the same entropy surface and a solution curve must lie wholly within a s

A reversible adiabatic path containing the initial state

surface.

The solution surfaces cannot intersect. If they did, states located

marked the division between the states that were points of intersection would have multiple values of entropy, and this

accessible or inaccessible from that state, with all violate a fundamental property of state functions. Thus, the surfaces

expected to be ordered monotonically, either systematically increasi

accessible states lying on one side of the reversible decreasing) as one proceeds in a given direction from surface to surface. F

purposes, let us assume Sl > $2 > $3 in Figure 2.12.

adiabatic path, and all inaccessible states lying on the Presumably all points on the same surface can be connected by

other side of it. solution curve (reversible adiabatic process). However, states on surface

example, cannot be connected to states on either S~ or $3 by any rev

2nd law of thermodynamics

In terms of the surfaces, the entropy surface on which an initial state resides

represents a division between accessible and inaccessible entropy surfaces.

The First and Second Laws of Thermodynamics 79

1 i

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.

respectively, with T2 > T1

The reservoirs are in thermal contact with each other through a large number of

intermediate temperature reservoirs, with the whole system thermally insulated

Reservoir Reservoir

at T1 at T2

Intermediate Reservoirs

The intermediate reservoirs are established so that the temperature of each differs from

that of its neighbors by increments small enough that heat transfer can be regarded as

taking place reversibly from intermediate reservoir to intermediate reservoir.

2nd law of thermodynamics

Reservoir Reservoir

at T1 at T2

Intermediate Reservoirs

The temperature difference between the outer reservoirs is a measurable one, heat will

flow spontaneously from the high-temperature reservoir through the intermediate

reservoirs to the low-temperature one

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

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

change is zero.

Given the convention that we have established for the sign of heat flow, we can state

that q2 < 0.

Because the overall system is isolated, q1, the heat flowing into the low- temperature

reservoir is given by q1 = -q2. This implies that q1>0

2nd law of thermodynamics

The First and Second Laws of Thermodynamics 81

Reservoir Reservoir

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

ql

Intermediate The

Reservoirs

AS1 = and Second Laws of Thermodynamics

First 81

T1 The First and Second Laws of Thermodynamics 81

reservoir. TheTheresult

the entropy change for eachand First and

is Second Laws of Thermodynamics 81

Since the heat was transferred reversibly out of the high-temperature reservoir and into

the entropy ql change for each reservoir. The result is

the low-temperature reservoir,

the = wechange

entropy

AS1 mayforuse

each these q2

reservoir.

AS2 quantities

= ~ . The result is to calculate the entropy

T1 T2

change for each reservoir. qlql

and AS1 ==

AS1 We have previously shown with complete generality that the entropy of a

T1

T1 composite system is the sum of the entropies of its components, and so we can

q2 write that

and

AS2 = ~ .

and T2

q~ q2

q2 AS-- t

AS2 = ~ . shown with complete

We have previously T1 generality

T2 that the entropy of a

T2 sum of the entropies of its components, and so we can

composite system is the q2

write that AS2 = ~ . which can be simplified to

We have previously

T2 shown with complete generality that the entropy of a

composite system is the sum of the entropies of its components, and so we can

q~ q2 q~ q~

write

A S - -that t

We have T1 T2 previously shown with =complete

AS . . . .

T1 7"2

ql I 1

T~

1 generality

7"2

1. that the

entropy of a

composite system q~ q2is the sum of the entropies of its components, and so we can

which can be A S--

simplified t to

write that T1 T2 Since ql > 0, and 1 / T l > l / T 2 with ~ > T1, we conclude that AS for this

allowed, spontaneous process is greater than zero. Having obtained this result

Since q1 > 0, and 1/T1 >1/T2 with T2 > T1, we conclude that ΔS for this spontaneous

which q~ beq~simplified

can

AS . . . . = ql for to

q~ Iq2

1

the specific case, we can extend it to the general case, because our earlier

conclusion1 1 . that there is an allowed direction to spontaneous adiabatic processes

process is greater than zero. AT1S - - 7"2 t applies

T~ 7"2

to all thermodynamic systems.

T1

q~

AS . . . .

q~ T2

= qlTo 1summarize

Since ql > 0, and 1 / T l > l / T 2 I with 1 1>. T1, we conclude that AS for this

~7"2

T1 7"2 T~

allowed, spontaneous process is greater than zero. Having obtained this result

for which can case,

the specific be simplified

we can extend todS(reversible adiabatic processes)- 0

it to the general case, because our earlier

2nd law of thermodynamics

There is an allowed direction to spontaneous adiabatic processes which applies to all

thermodynamic systems.

enclosed system

ΔS(universe) ≥ 0

and allowed, or irreversible and forbidden

thermodynamics

2nd law of thermodynamics

When the net entropy change is zero, the process is reversible, and the system is said

to be at equilibrium

If the total entropy is greater than zero, the process will occur. Such a process is often

referred to as a spontaneous or natural process. If the net entropy change is negative,

the process is unnatural and will not occur.

predicting the spontaneity or reversibility of a process.

MM209 - Thermodynamics

Instructor : Aswani Yella

43

2nd law of thermodynamics

MATHEMATICAL INTERLUDE III: PFAFFIAN DIFFERENTIAL FORMS

Note: It is obvious that two (reversible) adiabats cannot intersect. Once Carathéo-

dory’s Principle is accepted, the concept of entropy can be defined without recourse

toCaratheodary formulation of 2 law

nd

Carnot cycles by using mathematical properties of certain linear differential

equations called Pfaffian expressions, summarized in the following mathematical

interlude.

Avoids the use of cycles and heat engines

MATHEMATICAL INTERLUDE III: PFAFFIAN DIFFERENTIAL FORMS 43

Uses mathematical terms and axioms to develop 2nd law of thermodynamics

4.6

Note: MATHEMATICAL

It is obvious that two INTERLUDE III: PFAFFIAN

(reversible) adiabats cannot intersect. Once Carathéo-

DIFFERENTIAL

dory’s Principle isFORMS

accepted, the concept of entropy can be defined without recourse

to Carnot cycles by using mathematical properties of certain linear differential

Caratheodary

A differential

equations called Theorem

expression

Pfaffian of the form summarized in the following mathematical

expressions,

Ifinterlude.

a Pfaffian expression

dL ¼ !i Xi dxi ð4-24Þ

has the property for which, in the neighborhood of any point P, there are points that

where Xi isbea connected

4.6cannot function oftoINTERLUDE

MATHEMATICAL the variables

P along xIII:

curves 2 ; . . satisfy

1 , xthat

PFAFFIAN. ; xr , isthe

called a Pfaffian

equation dL = 0, then the

differential

Pfaffian form.

DIFFERENTIAL The

expression equation

FORMShas an integrating factor

dL ¼ !i Xi dxi ¼ 0 ð4-25Þ

A differential expression

A differential of theofform

expression the form

is called Pfaffian differential equation. The differential forms are sometimes

dL ¼ ! X dx ð4-24Þ

exact, although generally they are not.i i i

We consider

where X is a three special

function of cases.

the variables x2 ; x2,…xn,

x1 ,x1, . . . ; xr , isiscalled

where Xi is a function of the

i variables calledaaPfaffian

Pfaffian differential form

differential form. The equation

1) dL is exact. Then

4.6 MATHEMATICAL INTERLUDE III: PFAFFIAN

nd

DIFFERENTIAL FORMS 2 law of thermodynamics

A differential expression of the form

If a Pfaffian expression

dL ¼ !i Xi dxi ð4-24Þ

has the property for which, in the neighborhood of any point P, there are points that

where Xi isbea connected

cannot function oftothe variables

P along curves 2 ; . . satisfy

x1 , xthat . ; xr , isthe

called a Pfaffian

equation dL = 0, then the

differential form. The equation

Pfaffian expression has an integrating factor

dL ¼ !i Xi dxi ¼ 0 ð4-25Þ

From the Caratheodary theorem the following conclusions can be drawn

is called Pfaffian differential equation. The differential forms are sometimes

exact, although

(a) the generally

existence of anthey are not. denominator for the differential expression for a

integrating

We considerheat

reversible three specialthat

transfer cases.

transformed the inexact differential into an exact

differential, and thereby providing an operational definition for some state function

1) dL is exact. Then

(b) the general tendency of this state function to increase.

qXi =qxj ¼ qXj qxi for all i; j ¼ 1; 2; . . . ; r ð4-26Þ

This conclusion, which is another way of stating the Second Law, is known as the

An integrating

Caratheodory factor, "(x

principle. 1 , . .be

It can . ,xrstated

), is a as

factor that turns the inexact

differential

In the dL intoofanevery

neighborhood exactequilibrium

one, which statewe represent as ds. Writingsystem, there exist

of a thermodynamic

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

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

4.6 MATHEMATICAL INTERLUDE III: PFAFFIAN

DIFFERENTIAL FORMS

2nd law of thermodynamics

A differential expression of the form

If a Pfaffian expression

dL ¼ !i Xi dxi ð4-24Þ

has the property for which, in the neighborhood of any point P, there are points that

where Xi isbea connected

cannot function oftothe variables

P along curves 2 ; . . satisfy

x1 , xthat . ; xr , isthe

called a Pfaffian

equation dL = 0, then the

differential

Pfaffian form. The equation

expression has an integrating factor

dL ¼ !i Xi dxi ¼ 0 ð4-25Þ

Mathematically, it can be shown that a two-dimensional Pfaffian is either exact, or, if it is

is called

inexact,Pfaffian differential

an integrating equation. The

denominator candifferential

always beforms aretosometimes

found convert it into a new, exact,

exact, although generally they are not.

differential.

We consider three special cases.

1) dL is exact. Then

Caratheodory showed that expressions for dqrev fall into the class of inexact but

integrable differential

qXi =qxj ¼expressions.

qXj qxi for That all i; jis,¼an integrating

1; 2; ...;r denominator

ð4-26Þ exists that can

convert the inexact differential into an exact differential.

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

An integrating factor, "(x1 , . . . ,xr ), is a factor that turns the inexact

differential dL into an exact one, which we represent as ds. Writing

some examples involving only two variables. These do not provide the

generality we must have to treat thermodynamic systems of three or more

<.,-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

R:D

.~ .

⎜ ⎟

"~

⎝ ⎠Vm R

~

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

~1 ~

Vm

..a

~

~

2nd law of thermodynamics

According to the Caratheodory theorem, the existence of an integrating denominator

that creates an exact differential (state function) out of any inexact differential is tied to

the existence of points (specified by the values of their xi's) that cannot be reached

from a given point by an adiabatic path (a solution curve).

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

From a given thermodynamic state of the system, there are states that cannot be

reached from the initial state by way of any adiabatic process.

2nd law of thermodynamics

Let us define the system as being characterized by an empirical temperature, θ and any

other number of variables, x1,x2, ….xn

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

temperature T, and the other variable,

xj, will be the analogue of pressure p.

isotherms

2nd law of thermodynamics

Lets take two isotherms, θ1 and θ2, with θ2 < θ1

Lets take State 1, which is defined by θ1 and x1, can be connected to states 1' and 1"

by a series of reversible isothermal processes The First and Second Laws of Thermodynamics 69

isothermal path, and we will assume that this flow

of heat is a continuous function of x1 along the

isotherms, with the absorption or liberation

depending upon the direction in which x1 is varied.

Lets say heat is liberated in going from 1 to 1', then increasing amount of heat is

liberated on going from 1 to states farther and farther removed from 1 such as 1".

If the direction of the process is switched and the system proceeds from 1" to

1' or on to 1, heat would be absorbed in increasing amounts.

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

2nd law of thermodynamics

For each state identified on the θ1 isothermal as 1, 1', 1".... , let us draw paths

representing reversible adiabatic processes that intersect a second isotherm

at θ2. The First and Second Laws of Thermodynamics 69

from states 1, 1' and 1" on θ1 with those on θ2 are

denoted by 2, 2' and 2", respectively.

Along the three paths, 1-2, 1'-2', and 1"-2", no heat is absorbed or liberated because

the processes that connect these points are defined to be adiabatic.

We wish to show that no points to the left of 2 on the isotherm θ2 are accessible from

point 1 via any adiabatic path, reversible orFigure

irreversible.

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

pressure. (a) Reversible adiabatic paths (solid lines: 1 " ~ 2 " ; 1' ~ 2 ' ; and 1 ~ 2 )

connect states on two isothermal lines of a general thermodynamic system: An

irreversible adiabatic path (dotted line: 1 --~ 2') can be shown to be forbidden, while an

2nd law of thermodynamics

Suppose we assume that some adiabatic path does exist between 1 and 2'.

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

that arising from the last step 1’ - 1

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

Thus, for this process, w is negative (and therefore performed by the system), since q1’-1

is positive, having been absorbed from the reservoir.

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

pressure. (a) Reversible adiabatic paths (solid lines: 1 " ~ 2 " ; 1' ~ 2 ' ; and 1 ~ 2 )

connect states on two isothermal lines of a general thermodynamic system: An

irreversible adiabatic path (dotted line: 1 --~ 2') can be shown to be forbidden, while an

2nd law of thermodynamics

Thus, for this process, w is negative (and therefore performed by the system), since q1’-1

is positive, having been absorbed from the reservoir.

The First and Second Laws of Thermodynamics 69

completely convert heat absorbed at a high

temperature reservoir into work.

possible

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

path.

pressure. (a) Reversible adiabatic paths (solid lines: 1 " ~ 2 " ; 1' ~ 2 ' ; and 1 ~ 2 )

connect states on two isothermal lines of a general thermodynamic system: An

irreversible adiabatic path (dotted line: 1 --~ 2') can be shown to be forbidden, while an

2nd law of thermodynamics

What about points to the right of 2? Can they be reached?

Consider an adiabatic path from point 1 to point 2a that is also located onandthe

The First isothermal

Second Laws of Thermodynamics 69

θ2.

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

heat.

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

thermodynamics.

Thus, there are states to the right of 2 on the isotherm θ2of that

Figure 2.11 Graph are

empirical accessible

temperature from

0 against x, a state variable such as

pressure. (a) Reversible adiabatic paths (solid lines: 1 " ~ 2 " ; 1' ~ 2 ' ; and 1 ~ 2 )

1 via an adiabatic path. connect states on two isothermal lines of a general thermodynamic system: An

irreversible adiabatic path (dotted line: 1 --~ 2') can be shown to be forbidden, while an

2nd law of thermodynamics

Since the only constraint we have placed on θ2 is that it be less than θ1, the

second isotherm can be as arbitrarily close to the first as we wish.

There are states located in the plane defined by θ and x1 that are inaccessible from

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

state 1. (a) Reversible adiabatic paths (solid lines: 1 " ~ 2 " ; 1' ~ 2 ' ; and 1 ~ 2 )

pressure.

connect states on two isothermal lines of a general thermodynamic system: An

irreversible adiabatic path (dotted line: 1 --~ 2') can be shown to be forbidden, while an

There is aadiabatic

irreversible sense of pathdirection to the

(dashed line: 1 ~ location of the

2a) is allowed. (b) inaccessible states.

A reversible adiabatic

path through state 1 at temperature 01 divides the states at lower temperatures into two

State 2, the

regions, thosestate reached

that are accessiblefrom 1 by a reversible

via irreversible adiabatic

adiabatic paths and those path,

that arerepresents

the division

not.

between the states on the second isotherm that are accessible and inaccessible from

state

heat 1.

is liberated in going from 1 to 1', then increasing a m o u n t s of heat are

same state 1 as earlier. The value of x2 in state 1 will fix the location of this state

on the isotherm in the new direction. A reversible adiabatic path can be

2nd law of thermodynamics

constructed that connects state 1 with a state on the second isothermal in the x2

direction. Irreversible states located on one side of this point will be inaccessible

from state

Within the neighborhood 1 by adiabatic

of every paths,

state in this while states located

thermodynamic system,onthere

the are

otherstates

side of that

point will

that cannot be reached be accessible.

via adiabatic Thus, there exist states located on the plane defined by 0

paths.

and x2 that are inaccessible from point 1. Similar conclusions can be drawn by

considering isotherms localized on the planes formed by 0 and each of the xi.

Thus, we can conclude that, within the neighborhood of every state in this

Given the existence of these states, then, the existence of an integrating denominator

thermodynamic system, there are states that cannot be reached via adiabatic

for the differential element of reversible heat, dqrev, is guaranteed from Caratheodory's

paths. Given the existence of these states, then, the existence of an integrating

theorem.

denominator for the differential element of reversible heat, ~Sqrev, is guaranteed

from Carath6odory's

66 Chemical theorem.

Thermodynamics: PrinciplesOur next task is to identify this integrating

and Applications

denominator.

dqrev for an ideal gas undergoing only pressure-volume work is an inexact differential.

so that

2.2f The Identification of the Absolute (Ideal Gas) Temperature

RT

as(Sqrev

the-- Integrating

d Vm + Denominator

dT. (2.43)

We have previously Vm showna Tthat "mthe Pfaff differential ~Sq~v for an ideal gas

undergoing only pressure-volume work {equation (2.43)} is an inexact

Applying the

differential. It condition

is easy toforshow

exactness

that gives"

division of equation (2.43) by the absolute

We can easily show that division

temperature of above

T yields equation

an exact by the expression.

differential absolute temperature

The divisionT gives

yields an exact differential expression.

qrev R R

= ~ d Vm + - d T. (2.45)

T OTVm VmT aT

undergoing only pressure-volume work {equation (2.43)} is an inexact

differential. It is easy to show that division of equation (2.43) by the absolute

2nd law of thermodynamics

temperature T yields an exact differential expression. The division gives

qrev R

= ~ d Vm + - d T. (2.45)

T Vm T aT

Application of the for exactness

condition for shows thatshows

exactness both derivatives equal zeroequal

that both derivatives

zero, so equation (2.45) must be exact. Thus, we have determined that when an

ideal⎛⎜ ∂gas

⎛ R ⎞is⎞ involved, T is an integrating denominator for ~Sqrev, and the right

⎜ ⎟⎟ ⎛ 1 ⎞⎛ ∂ ⎛ ∂U m ⎞ ⎞ ⎛ 1 ⎞⎛ ∂ ⎛ ∂U m ⎞ ⎞

hand⎜ side⎝ Vm ⎠ of

⎟ equation (2.45) ⎜is ⎟the

⎜ total

⎜ ⎟differential

⎟ = ⎜ ⎟⎜⎜ for ⎜ a⎟ state

⎟⎟ = 0function that we

=0 ⎝ T ⎠ ∂V

⎝ m ⎝ ∂T ⎠ ⎝ T ⎠ ∂T ∂V

⎜ ∂T ⎟ Vm ⎠T ⎝ ⎝ m ⎠T ⎠Vm

will represent as dS. cc

⎜ ⎟

What

⎝ we

⎠Vm must consider now is the generality of the result obtained for the

special case of the ideal gas. We define a new thermodynamic system that is the

When an ideal gas is involved, T is an integrating denominator for dqrev

cc We should remember that an integrating denominator for all inexact differential expressions in

two dimensions is guaranteed. Hence, its existence for the differential reversible heat element is

not unexpected.

Caratheodary has indeed shown that absolute temperature functions equally well as an

integrating factor not only the ideal gas but for the most complex systems also

2nd law of thermodynamics

The Caratheodory treatment is grounded in the mathematical behavior of Pfaffian

differential expressions, and the observation that a differential element of heat for a

reversible process can be written in this form, where the dxi's represent state variables.

It is not generally possible to write such expressions for the differential element of heat

for irreversible processes, and therefore, an integrating denominator does not exist for

irreversible processes.

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

to reversible processes.

2nd law of thermodynamics

For reversible processes, dqrev is an inexact Pfaffian differential expression, and dS

is an exact one

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

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

is satisfied

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

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

the entropy surface, S2

Figure entropy.

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

curve marked (Sqrev = 0 represents a reversible adiabatic path that connects two

that lie on the entropy surface, $2. The dashed curves marked ~Sqirr = 0 are irrev

paths that connect states on different entropy surfaces. Only one of these two pa

be allowed; the other will be forbidden.

dS = 0 for a reversible adiabatic process because dqrev = 0.

it is easy to see that dS = 0 for a reversible adiabatic process because ~ q r e

Two points which can be connected by a reversible adiabatic path must

Two points which can be connected by a reversible adiabatic path must lie on the same

the same entropy surface and a solution curve must lie wholly within a s

surface.

entropy surface and a solution curve must lie wholly within a solution surface.

The solution surfaces cannot intersect. If they did, states located

points of intersection would have multiple values of entropy, and this

violate a fundamental property of state functions. Thus, the surfaces

expected to be ordered monotonically, either systematically increasi

All points on the same surface can be connected by some solution curve (reversible

decreasing) as one proceeds in a given direction from surface to surface. F

adiabatic process). purposes, let us assume Sl > $2 > $3 in Figure 2.12.

Presumably all points on the same surface can be connected by

solution curve (reversible adiabatic process). However, states on surface

example, cannot be connected to states on either S~ or $3 by any rev

2nd law of thermodynamics

All points on the same surface can be connected by some solution curve (reversible

adiabatic process).

The First and Second Laws of Thermodynam

1 i

States on surface S2, cannot be connected to states on The First and Second Laws of Thermodynamics

r:v I

69

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

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

Sl >

We have shown previously that for any given initial state there are states that are

curve marked (Sqrev = 0 represents a reversible adiabatic path that connects two

that lie on the entropy surface, $2. The dashed curves marked ~Sqirr = 0 are irrev

accessible via adiabatic paths from the initial state, as well as states that are

paths that connect states on different entropy surfaces. Only one of these two pa

be allowed; the other will be forbidden.

inaccessible from that initial state by way of adiabatic paths.

it is easy to see that dS = 0 for a reversible adiabatic process because ~ q r e

Two points which can be connected by a reversible adiabatic path must

the same entropy surface and a solution curve must lie wholly within a s

A reversible adiabatic path containing the initial state

surface.

The solution surfaces cannot intersect. If they did, states located

marked the division between the states that were points of intersection would have multiple values of entropy, and this

accessible or inaccessible from that state, with all violate a fundamental property of state functions. Thus, the surfaces

expected to be ordered monotonically, either systematically increasi

accessible states lying on one side of the reversible decreasing) as one proceeds in a given direction from surface to surface. F

purposes, let us assume Sl > $2 > $3 in Figure 2.12.

adiabatic path, and all inaccessible states lying on the Presumably all points on the same surface can be connected by

other side of it. solution curve (reversible adiabatic process). However, states on surface

example, cannot be connected to states on either S~ or $3 by any rev

2nd law of thermodynamics

In terms of the surfaces, the entropy surface on which an initial state resides

represents a division between accessible and inaccessible entropy surfaces.

The First and Second Laws of Thermodynamics 79

1 i

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.

respectively, with T2 > T1

The reservoirs are in thermal contact with each other through a large number of

intermediate temperature reservoirs, with the whole system thermally insulated

Reservoir Reservoir

at T1 at T2

Intermediate Reservoirs

The intermediate reservoirs are established so that the temperature of each differs from

that of its neighbors by increments small enough that heat transfer can be regarded as

taking place reversibly from intermediate reservoir to intermediate reservoir.

2nd law of thermodynamics

Reservoir Reservoir

at T1 at T2

Intermediate Reservoirs

The temperature difference between the outer reservoirs is a measurable one, heat will

flow spontaneously from the high-temperature reservoir through the intermediate

reservoirs to the low-temperature one

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

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

change is zero.

Given the convention that we have established for the sign of heat flow, we can state

that q2 < 0.

Because the overall system is isolated, q1, the heat flowing into the low- temperature

reservoir is given by q1 = -q2. This implies that q1>0

2nd law of thermodynamics

The First and Second Laws of Thermodynamics 81

Reservoir Reservoir

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

ql

Intermediate The

Reservoirs

AS1 = and Second Laws of Thermodynamics

First 81

T1 The First and Second Laws of Thermodynamics 81

reservoir. TheTheresult

the entropy change for eachand First and

is Second Laws of Thermodynamics 81

Since the heat was transferred reversibly out of the high-temperature reservoir and into

the entropy ql change for each reservoir. The result is

the low-temperature reservoir,

the = wechange

entropy

AS1 mayforuse

each these q2

reservoir.

AS2 quantities

= ~ . The result is to calculate the entropy

T1 T2

change for each reservoir. qlql

and AS1 ==

AS1 We have previously shown with complete generality that the entropy of a

T1

T1 composite system is the sum of the entropies of its components, and so we can

q2 write that

and

AS2 = ~ .

and T2

q~ q2

q2 AS-- t

AS2 = ~ . shown with complete

We have previously T1 generality

T2 that the entropy of a

T2 sum of the entropies of its components, and so we can

composite system is the q2

write that AS2 = ~ . which can be simplified to

We have previously

T2 shown with complete generality that the entropy of a

composite system is the sum of the entropies of its components, and so we can

q~ q2 q~ q~

write

A S - -that t

We have T1 T2 previously shown with =complete

AS . . . .

T1 7"2

ql I 1

T~

1 generality

7"2

1. that the

entropy of a

composite system q~ q2is the sum of the entropies of its components, and so we can

which can be A S--

simplified t to

write that T1 T2 Since ql > 0, and 1 / T l > l / T 2 with ~ > T1, we conclude that AS for this

allowed, spontaneous process is greater than zero. Having obtained this result

Since q1 > 0, and 1/T1 >1/T2 with T2 > T1, we conclude that ΔS for this spontaneous

which q~ beq~simplified

can

AS . . . . = ql for to

q~ Iq2

1

the specific case, we can extend it to the general case, because our earlier

conclusion1 1 . that there is an allowed direction to spontaneous adiabatic processes

process is greater than zero. AT1S - - 7"2 t applies

T~ 7"2

to all thermodynamic systems.

T1

q~

AS . . . .

q~ T2

= qlTo 1summarize

Since ql > 0, and 1 / T l > l / T 2 I with 1 1>. T1, we conclude that AS for this

~7"2

T1 7"2 T~

allowed, spontaneous process is greater than zero. Having obtained this result

for which can case,

the specific be simplified

we can extend todS(reversible adiabatic processes)- 0

it to the general case, because our earlier

2nd law of thermodynamics

There is an allowed direction to spontaneous adiabatic processes which applies to all

thermodynamic systems.

enclosed system

ΔS(universe) ≥ 0

and allowed, or irreversible and forbidden

thermodynamics

2nd law of thermodynamics

When the net entropy change is zero, the process is reversible, and the system is said

to be at equilibrium

If the total entropy is greater than zero, the process will occur. Such a process is often

referred to as a spontaneous or natural process. If the net entropy change is negative,

the process is unnatural and will not occur.

predicting the spontaneity or reversibility of a process.

:AA b\dA:

!d: \ p A A

) YA !bgpYA \2\__ )A _gA 8 p A A

:AA b\dA:!d: YA ) YA !bgpYA \2 p A A !d: YA

Y\nd

g\)_A

A\QY

YAd

Y! gJ: \dQ

: gp3.5)A_g

YA p\gdu

\ _\b!A

AN ILLUSTRATION \8 !d: 2 law of thermodynamics

Ap!d\gd

\ AAd pg\)_A

46 Introduction to the Thermodynamics of Materials

gA Ygg pg\\gd8

!JA gbA

OF IRREVERSIBLE

YA p\gd

YAd

Y!b!

g2\__!\gd

: \dQ Y\ Ap!d\gd YA p\gd b!

46 Introduction to the Thermodynamics of Materials

: gp3.5)A_g

AND REVERSIBLE AN ILLUSTRATION \8 !d: !JA gbA

OF IRREVERSIBLE g2\__!\gd

AND REVERSIBLE

PROCESSES PROCESSES

rYAYA

A_A :gd Y\ILLUSTRATION

g

!2!__

\ Kd!_ Y!ppAd OF REVERSIBLE

pg\\gdu ! Q\Ad AND

\d rYAYA Y\IRREVERSIBLE

2!A !2!__ Y!ppAd PROCESSES

\d ! Q\Ad 2!A

Consider a system of water and water vapor at the uniform temperature T contained Consider

in a a system of water and water vapor at the uniform temperature T contained in a

cylinder fitted with a frictionless piston, and let the cylinder be placed in thermal contact

cylinder

with afitted with a frictionless piston, and let the cylinder be placed in thermal contact with a

The permanent change in the external agency caused by the cyclic process carried out

heat reservoir which is also at the constant temperature T. This system is shown in heat

Fig.reservoir

3.2 which is also at the constant temperature T. This system is shown in Fig. 3.2

irreversibly is 2ΔPV.

Figure 3.2 A thermostalled piston and cylinder containing water and

YA3.2Q! \d YA p\gd r!s \ :AA b\dA: ) YA

A thermostalled piston and cylinder containing water and

water vapor.pg:A \d YA p!du J YA ! \ AbgA: water vapor. YA Q! Ap!d: ::Ad_ !d: \ AA \)

!

The water vapor in the cylinder Kd!_ of

exerts a !A

δP,r)suthen

certain pressure J the Q!

YA ,more

which nearly

Ap!d:

The

equal are

the vapor _g_8

iswater in the cylinder)

the

Abg\dQ

exerts

two work gdA

a certain pressure

terms,

p! \2_A and

, which isgJthein

_A!: pg

the limit

saturated vapor that

pressurethey

of waterare

at theequal,

temperatureno permanent

T. The system is exactly change

saturated occurs

at vapor pressure of waterinat the external

the temperature agency,

T. The and

system is exactly at

YApressure

equilibrium when the external p g2A acting on\the AA \)_A

piston, P , equals r2su

theequilibrium

ext

internal when the external pressure acting on the piston, P , equals the internal ext

hence the cyclic process

pressure acting on the piston,

has been conducted reversibly.

pressure acting on the piston,

, and when the temperature of the water+water , and when the temperature of the water+water

vapor in the cylinder equals the temperature T of the constant-temperature heat reservoir.

vapor in the cylinder equals the temperature T of the constant-temperature heat reservoir.

If the external pressure acting on the piston, Pext is suddenly decreased by a finiteIf amount

the external pressure acting on the piston, Pext is suddenly decreased by a finite amount

Thus, reversibly,

degradation, where is =process

whichqrev

if the evaporation U+was

given . If

is(q

max

the processreversibly,

conducted

–q)=(w is–w),

carried out irreversibly,

then

accounts heat

for q

the then less heat

leaves

fact that the

less qheat

heat is

Az\_\) \b

is transferred \Y \

from the reservoir to the gd:\dQu

rev

cylinder, where q=

max

U+w.AbpA ! Arev \__ )A Y! gJ \ gd:

The difference between

reservoir and enters

transferred the

to the cylinder

cylinder at thethe

from temperature

reservoir T. Theduring

during change

the in the entropy

irreversible process ofthan

the is

the work

!d:

transferred

heat reservoir is

done

\

during

given 2

during

the

by

nd law of thermodynamics

the reversible

p A A

reversible

Eq. (3.1)

\__

as

process

)A

process.

and that done

_gA 8 :AA b\dA:the irreversible

) YAprocess,

!bgpYA \2 p A A !d:

(wmax w), is the mechanical energy which has been degraded to thermal energy (heat) in

Thus,A\QY gJ YA p\gdu

if the evaporation process isconducted

\ AAdreversibly,

pg\)_A thenY!

heat : \dQ

q leavesY\ Ap!d\gd YA p\gd

the heat

the cylinder as a result of the irreversible nature of the process.46This heatrev

Introduction produced by of Materials

to the Thermodynamics

gA Ygg

reservoir and enters

degradation, which is \

thegiven_\b!A

cylinder

as (qrev the pg\\gd8

at–q)=(w

temperature

max

YAd

T. The

–w), accounts : gp

forchange )A_g

3.5in

the fact the

that

AN \8 is!d:

entropy

less heat

ILLUSTRATION the!JA gbA

of IRREVERSIBLE

OF g2\__!

AND REVERSIBLE

Consider only

heat reservoir the evaporation

is given by Eq. (3.1) asprocess PROCESSES

A_Ato :gd

transferred g from

the cylinder \ Kd!_ pg\\gdu

the reservoir rYAYA

during the irreversible Y\ process !2!__

than is Y!ppAd \d ! Q\Ad

transferred during the reversible process. Consider a system of water and water vapor at the uniform temperature T contained i

cylinder fitted with a frictionless piston, and let the cylinder be placed in thermal contact wi

Thus, if the evaporation process is conducted reversibly, then heat

heatreservoir leaves

qrev which theat heat

is also the constant temperature T. This system is shown in Fig.

If the evaporation process is conducted reversibly, then heat qrev leaves

reservoir and enters the cylinder at the temperature T. The change in the entropy of the

the heat

wherereservoir

the negative

andissign

heat reservoir enterscorresponds

given bythe

to heat leaving the heat reservoir, and thus the

Eq. cylinder

(3.1) as at the temperature T

entropy of the reservoir decreases. The change in the entropy of the water and water

vapor in the cylinder is

where the negative sign corresponds to heat leaving the heat reservoir, and thus the

entropy of the reservoir decreases. The change in the entropy of the water and water

vapor in the cylinder is

where the negative sign corresponds to heat leaving the heat reservoir, and thus the

where theentropy

positive signreservoir

of the corresponds to heat

decreases. The entering

change inthe

thecylinder, and

entropy of thethus theand

water entropy

water of

the contents

vaporofinthe

the cylinder

cylinder isincreases. The change in the entropy of the combined water-

vapor-heat reservoir system is thus

where the positive sign corresponds to heat entering the cylinder, and thus the entropy of

the contents of the cylinder increases. The change in the entropy of the combined water-

vapor-heat reservoir system is thus

where the positive sign corresponds to heat entering the cylinder, and thus the entropy of

This zero thechange

contentsinofentropy is due

the cylinder to the The

increases. fact

uthatYA

changethe

in process

p A A

the was

entropy of\dcarried

theYA out \d

Q!

combined reversibly,

YA p\gd r!s \ :AA b\dA:

water-

Figure 3.2 A thermostalled piston and cylinder containing water and

i.e., no degradation occurred

vapor-heat reservoir during

system the process.

ispg:A

thus \d YA p!du J YA ! \ AbgA: water vapor. YA Q! Ap!d: ::Ad_ !d:

If the evaporation is carried out irreversibly then heat q (q<qrev) is transferred from the

This zero change in entropy g ! Kd!_

is due !A

to the factr)su

that J

theYA Q!The

process Ap!d:

water vapor _g_8

was

saturated carried in the cylinder) Abg\dQ

exerts

outofreversibly,

vapor pressure

gdA p! \2_A

a certain pressure , which isg

water at the temperature T. The system is exactly

reservoir to the cylinder. The change in the entropy of the heat reservoir is thus

i.e., no degradation occurred YA during the process.

p g2A \ AA \)_A r2su equilibrium when the external pressure acting on the piston, Pext, equals the inter

If thezero

This evaporation

change in is carried

entropy is out

due irreversibly then

to the fact that the heat q (q<q

process was ) acting

is transferred

carried

pressure out piston, from ,the

reversibly,

on the and when the temperature of the water+wa

!d: \ p
A
A \__ )A _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

TheHowever,

total heat appearing

the total ininthe

heat appearing cylinder

the cylinder equals

equals the heatthe heat qfrom the

q transferred

transferred from

heat reservoir plusthe heatwhich

the heat reservoir plus

is produced by the heat which

degradation of work is due to the

irreversible nature of the process. Thus degraded work, (wmax–w), equals (qrev– q), and

produced by degradation of work due to the irreversible

thus the change in the entropy of the contents of the cylinder is

nature of the process.

However, the total heat appearing in the cylinder equals the heat q transferred from the

heat reservoir plus the heat which is produced by degradation of work due to the

Thus nature

irreversible degraded

of thework, (wmax

process. –w),

Thus equals work,

degraded (qrev–(w

q), and

–w), equals (qrev– q), and

max

thuswhich,

the itchange in theq entropy

is seen, is simply /T. Thus theofchange

the incontents

the entropy of the

of the combined system

thus the change in the entropy of the contents of the cylinder is

rev

cylinder is

caused by the irreversible nature of the process is

water vapor.

which, it is seen, is simply qrev/T. Thus the change in the entropy The

of water

the combined system

vapor in the cylinder exerts a certain pressure , which is

saturated vapor pressure of water at the temperature T. The system is exactly

caused by the irreversible nature of the process is equilibrium when the external pressure acting on the piston, Pext, equals the inte

As qrev>q, this entropy change is positive, and thus entropy has been produced (or

pressure acting on the piston, , and when the temperature of the water+w

created) as a result of the occurrence of an irreversible process. The entropy

vapor in produced,

the cylinder equals the temperature T of the constant-temperature heat reserv

(qrev–q)/T, is termed Sirreversible ( Sirr) and is the measure of the degradation which

If the external has acting on the piston, Pext is suddenly decreased by a finite amo

pressure

irreversible nature of the process. Thus degraded work, (wmax–w), equals (qrev– q), and

thus the change in the entropy of the contents of the cylinder is

2nd law of thermodynamics

which, it is seen, is simply qrev/T. Thus the change in the entropy of the combined system

Thus the change in the entropy of the combined system caused by the irreversible

caused

nature of by the irreversible

the process is nature of the process is

which, it is seen, is simply qrev/T. Thus the change in the entropy of the combined system

caused by the irreversible nature of the process is

As qrev>q, this entropy change is positive, and thus entropy has been produced as a

As q >q, this entropy change is positive, and thus entropy has been produced (or

result of the revirreversible process

created) as a result of the occurrence of an irreversible process. The entropy produced,

(q>q,

As qrev

rev

–q)/T, is termed

this entropy changeSirreversible ( Sirrand

is positive, ) and

thus is the measure

entropy has of theproduced

been degradation

(or which has

The entropy

created) as aproduced,

occurred result (qreoccurrence

as aofresult

the v–q)/T,

of is of

termed

the process. anThus, ΔSfor

irreversible ( ΔSirrThe

theprocess.

evaporation

irreversible ) and is theproduced,

entropy

process, measure of of the

irrespective

the(qdegradation which Shas occurred

–q)/T, is termed ( Sirras a result

) and of the process

is the measure of the degradation which has

rev degree of irreversibility,

irreversible

occurred as a result of the process. Thus, for the evaporation process, irrespective of the

For the evaporation

degree process, irrespective of the degree of irreversibility,

of irreversibility,

(3.2)

(3.2)

Consideration of the condensation process shows that the work done on the system has a

2nd law of thermodynamics

If we consider the condensation process, the work done on the system has a minimum

value when the condensation is conducted reversibly, and, correspondingly, the heat

transferred from the cylinder to the heat reservoir has a minimum value qrev.

performed, and the excess of this work over the minimum required is the work which is

degraded to heat in the irreversible process.

50 Introduction to the Thermodynamics of Materials

Thus,

Forfor a reversiblecondensation

a reversible condensation

and

For an irreversible condensation,

2nd law of thermodynamics

i.e., entropy is not created.

For an irreversible condensation,

For an irreversible condensation,

and

d, as q>qrev, it is seen that entropy has been created as a result of the irreversible

ocess. The entropy created is Sirr, and, thus, again, the change in the entropy of the

ter and water vapor is given by And, as q>qrev, it is seen that entropy has been created as a result of the irrevers

process. The entropy created is Sirr, and, thus, again, the change in the entropy of

water and water vapor is given by (3.3)

e important feature to be noted from Eqs. (3.2) and (3.3) is that, in going from an (3

ial state to a final state [either the evaporation or condensation of 1 mole of water at

and

e total heat appearing in the nd

2 law of thermodynamics

cylinder equals the heat q transferred from the

r plus the heat which is produced by degradation of work due to the

ature of the process. Thus degraded work, (wmax–w), equals (qrev– q), and

i.e., entropyFor

is not

the created.

condensation case

For the evaporation case

ge in the entropy of the contents of the cylinder is For an irreversible condensation,

een, is simply qrev/T. Thus the change in the entropy of the combined system

In both the cases, in going from an initial state to a final state, the left-hand sides are

e irreversible nature of being

constants, the process is respectively, to qrev/T and -qrev/T.

equal,

The difference in the entropy between the final and initial states is thus independent of

whether the process is conducted reversibly or irreversibly and, being independent of

the process path can be considered as The

being the difference between the values of a

andSecond Law of Thermodynamics 51

state function

(3.4a)

his entropy change is positive, and thus entropy has been produced (or

result of the occurrence of an irreversible process. The entropy produced,

termed Sirreversible ( Sirr) and is the measure of the degradation which has (3.4b)

result of the process. Thus, for the evaporation process, irrespective of the

Eq (3.4b) indicates that, as the change in entropy

versibility, canasbeq>q

And, determined

, it is only

seenbythat

measure-

entropy has been created

rev

2nd law of thermodynamics

ILLUSTRATION OF REVERSIBLE AND IRREVERSIBLE PROCESSES

2. The free expansion of an ideal gas.

These two processes have in common that the temperature of the gas remains

constant.

Since the gas is ideal, the internal energy of the gas does not change for either

process, since the temperature does not change

In the reversible case, work is performed by the gas during its expansion, but no work

is performed by the gas during the free expansion

From the First Law,

2nd law of

∆U thermodynamics

= q−w

We haveReversible Isothermal

seen that Expansion

the internal energyofofananIdeal Gas

ideal gas depends only on its tempera-

ture. Hence, ∆ U = 0, the

Let us consider andreversible

thus, q =isothermal

w ; that is,expansion

the work done by the

of 1 mole of aexpanding

monatomicgas on

ideal

gas from the state (VA,T) to the state (VB,T), where VB > VA

VB

Sand

VA 1 mole of

1 mole of an ideal gas

an ideal gas

(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

change T the entropy

in VAof the reservoir is

qrevq wrev VB VA

given by ∆ S = S B − S

∆gasSheat reservoir =

A= − == −∆ = R ln

S = RVln <0

TT T gas A VB

ch is also a positive quantity. The change in the entropy of the reservoir

qplus heat VAcanofbe

n bywhich

The is alsochange

total a positive

in ∆ Squantity.

the entropy

heat reservoir

The

(gas

= − change

= −∆ in reservoir)

Sgas

the

= entropy

R ln < 0 thewritten

reservoir

as is

given by T VB

∆Stotal = ∆Sgas + ∆Sreservoir = 0 (3.2)

The total change in the entropy (gas q heat reservoir)

q plus VA canVbe

A written as

2nd law of thermodynamics

Free Expansion of an Ideal Gas

consider the free expansion (i.e., expansion against zero atmospheric pressure) of 1

mole of an ideal gas from VA to VB.

The final state of the free expansion is the same as the state of the isothermal

reversible expansion process

2nd law of thermodynamics

Since entropy is a state function, the change of entropy of the gas for the free

expansion must be the same as that for the isothermal expansion.

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

In going from state A to state B, q

∆S = SB − S A = + ∆Sirr

T

q

= rev

T

2nd law of thermodynamics

Reversible Isothermal Compression

the state (VB,T) to the state (VA,T)

If the gas passes through a continuum of equilibrium states in going from the state

(VB ,T) to the state (VA ,T), then

Entropy is 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

2nd law of thermodynamics

Entropy changes for an ideal gas

2nd law of thermodynamics

ideal gas

I 5? T

V')

q - nRTln -.

AS-- ~dT.

V1

T T

84 Chemical Thermodynamics: Principles and Applications

H e n c e Isothermal Expansion of an Ideal Gas:

Calculation of ΔS for the Reversible

Calculation of AS for the Isochoric Temperature Change

dSIp

nR _

6q-Cv ~G

l ndT

AS-

I

dS-~

.

V1

CvdT

•SqrevExpansion:

Calculation of ΔS for the Reversible Adiabatic

Calculation of AS T

T for the Reversible Adiabatic Expansion

~Sq-O

5?

dS-0

T

I d_~Ttv Cv

Calculation of ΔS for the Isobaric Temperature Change:

AS-O.

T

AS-- ~dT.

Calculation of AS

T Tfor the Isobaric Temperature Change: k

I O_~Tt

v Cv

~Sq- Cp d r T

Calculation of AS for the Isochoric Temperature

Calculation of ΔS for the Isochoric Temperature Change: Chang

•Sqrev

6q-Cv dTT Cp d T

As-JTIC~T

d S - ~ = ~ dT.

T T

CvdT

Calculation of AS for the Reversible (Equilibrium) Phase

nd of a liquid at its melting point, a (solid + solid) phase

2 law of thermodynamics

freezing

transition temperature, and the boiling of a liquid or subliming

gas at a temperature where the vapor pressure of the liquid or s

ΔS for the Reversible (Equilibrium) Phase Change:

the confining atmospheric pressure, are reversible processes

The boiling of aconstant

liquid or subliming of a solidand

temperature to a pressure.

gas at a temperature where the

The entropy change for th

vapor pressure of the liquid or solid is equal to the confining atmospheric pressure, are

easily calculated. Integrating equation (2.38) at constant T give

reversible processes that occur at constant temperature and pressure.

The First and Second Laws of The

AS-- ~ =

At constant pT T

AtAt constant

constant

p

qrev --P A H

so that qrev -- A H

so thatAS = ~A,H

T

where ΔH, the change in enthalpy for theAchange

H in phase

where AH,AS the

= ~change

, in enthalpy for the change in phase,

T AvapH, the enthalpy of vaporization, /Xtr~n~

enthalpy of fusion,

moles of ideal gas B at the same pressure p and temperature 7

stopcock is opened, the gas molecules mix spontaneously and irrev

2nd law of thermodynamics

an increase in entropy Ami• occurs. The entropy change can be c

recognizing that the gas molecules do not interact, since the gas

AmixS is then simply the sum of ASA, the entropy change for the e

ΔS for the Mixing of Ideal Gases gas

at Constant

A from VA T and P:+ VB) and/XSB, the entropy change for the e

to (VA

gas B from VB to (VA + V~). That is,

Consider the process where nA moles of ideal gas A are confined in a bulb of volume VA

at a pressure p and temperature T. This bulb is separated by a valve or stopcock from

m m i x S - ASA --1-A S B.

bulb B of volume VB that contains nB moles of ideal gas B at the same pressure p and

temperature T

A B A+B

molecules mix spontaneously and irreversibly .~ O | |

0 | |

I"Io

Order AS > 0 Disorder

Increase in entropy occurs.

Figure 2.13 Mixing of ideal gas A with ideal gas B at constant tem

constant total pressure. The entropy change AS is given by equation (2.

The entropy change can be calculated by recognizing that the gas molecules do not

interact, since the gases are ideal.

an increase in entropy Ami• occurs. The entropy change c

nd2 law of thermodynamics

recognizing that the gas molecules do not interact, since

AmixS is then simply the sum of ASA, the entropy change f

gas A from VA to (VA + VB) and/XSB, the entropy change f

ΔmixS is then simply the sum of ΔSA, the entropy change for the expansion of gas A

from VA to (Vgas88 B fromThermodynamics"

Chemical VB to (VA + V~).

Principles That is,

A + VB) and ΔSB, the entropy change for the expansion of gas B from VB to

and Applications

(VA+ VB).

88 Chemical Thermodynamics" Principles and Applications

m m i x Schanges

The entropy - ASA ASA--1-

andA SASBB. can be calculated from equation (2.69),

which applies

The entropy to the

changes ASAisothermal

and ASB can reversible

be calculatedexpansion

from equationof ideal

(2.69), gas, since AS is

independent

which applies to theofisothermal

the pathreversible

and theexpansion

same result

of idealisgas,

obtained

since AS for

is the expansion

The entropy independent

changes

during ΔS the and B can

spontaneous

of Athe ΔSand

path be calculated

the mixing

same process

result byasusing

is obtained for the

during expression

the the controlled

expansion for reversible

isothermal reversible

during the expansion

expansion.spontaneous

Equationof ideal

mixing gas.

process

(2.69) givesas during the controlled reversible

expansion. Equation (2.69) gives A B A+B

ASA ASA

VA + V~VA

- r/A R- In r/A R In

VA VA

+ V~

o eoL o |

.~ O | |

0 | |

I"Io

VA+ VB

A S B -- nBR In VA+ VB

A S B -- nBR In

Hence

Order AS > 0 Disorder

Hence

I VA + VB VA + VB

AmixS- R rtA In + nB In

. (2.75)

Figure 2.13 Mixing of ideal gas VA

I VA A + with

VA + VB

VB VBideal gas B at const

A m i x S - R rtA In + nB In

. (2.75)

constant total pressure. The entropyVBchange AS is given by equa

VA

Using the ideal gas equation, we can write

I RT

VA + VB VA + VB

A m i x S - R rtA In + nB In

ndThermodynamics"

. pVB (2.75)

2 law

88 Chemical

n A - -of

VA

thermodynamics

PVA

~ p(VA + VB)

VB and Applications

Principles

/7B --

Using thethe

ideal gasgas

equation,

nA + n B - -

we we RT

can can

write

RT

Using ideal equation, write

R TASB can be calculated from equation (2.69),

The entropy changes ASA and

pVB reversible expansion of ideal gas, since AS is

which applies to the isothermal

PVA p(VA + VB)

n A - - ~independent of the/7B path

-- and the samenAresult is obtained for the expansion

Combining the last + n B --

RT

during the spontaneous Tthreeprocess

Rmixing equations

as duringgives

the controlled reversible

RT

expansion.

pVB Equation (2.69) gives

/7B --

RT nA p(VA + VB)

VA

nA +=VA

n B+- Combining

-V~

ASA - r/A R In =XA the last three equations give

p(VA h+AVB)

+riB VA

V A + VB

RT

nA + n B - -

RT VA+ VB

CombiningnBR In the last

A S B -- nB nA

VBthree equations givesVA

Combining the last three equations =gives = = XB =XA

nA -]- nBnA VA -+- VB hA+riB V A + VB

Hence VA

nA VA = =XA

= =XA (2.76)

nB VB

B9

hA+riB V A + VB hA+riB V A + VB

0

0

whereAXA and I XB are

m i x S - R rtA In

VA +the

VB mole VA

+ nB In

fractions

+ VB

=. of A and =B XBin the mix

(2.75)

nB equations (2.76) andVA (2.77)VB nAinto

-]-VBnBequation-+-(2.75) and rearr

VB

= = XB nB VA (2.77)

VB

~ I~.

c~

= = XB

m

o

nA -]- nB VA -+- VB

nAequation,

Using the ideal gas -]- nB weVAcan-+-write

VB

oe

.,..

A and BXA and XB Substituting

are the mole fractions

-..

in the mixture.

equations (2.76) and (2.77)

PVAinto equation (2.75) and rearranging gives the

:~

~

I

i.

2nd law of thermodynamics

2nd law of thermodynamics

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

to reversible processes.

process would not yield an entropy change for the process.

Entropy is a state function, the changes associated with irreversible processes can still

be calculated if a reversible path, perhaps a purely hypothetical one, can be conceived

for which dqrev/T can be evaluated.

2nd law of thermodynamics

1. Entropy is a thermodynamic state variable (function).

2. Entropy is not created when a system undergoes a reversible process; entropy is

transferred from one part of the system/surroundings to another part.

3. The total entropy of the universe increases when an irreversible process occurs.

4. For all processes, we can write ∆S′ = q/T + ∆Sirr′ and q ≤ qrev system.

5. For all processes, the entropy of the universe increases or stays the same. The

total entropy of the universe never decreases.

MM209 - Thermodynamics

Instructor : Aswani Yella

2nd law of thermodynamics

Conversion of heat into work

When two stones are rubbed together under water, the work done against the

force of friction is transformed into internal energy tending to produce a rise

of temperature of the stones.

above that of the surrounding water, however, there is heating of the water.

If the mass of water is large enough, then there will be no appreciable rise of

temperature, and the water can be regarded as a heat reservoir

Since the state of the stones is the same at the end of the process as

at the beginning, the net result of the process is merely the conversion of

mechanical work into heat.

2nd law of thermodynamics

Conversion of heat into work

water or in a very large mass of water, there is also a conversion of electrical work into

heat, without any change in the thermodynamic coordinates of the wire.

Work of any kind W may be done on a system in contact with a reservoir, causing heat Q

to leave the system without altering the state of the system.

The system acts merely as an intermediary. It is apparent from the first law that the work

is equal to the heat, W = Q;

The transformation of work into heat is accomplished with 100 percent efficiency.

Moreover, this transformation can be continued indefinitely.

2nd law of thermodynamics

Conversion of work into heat

discussing the conversion of heat into work.

In this case, there is no change of internal energy, since the temperature remains

constant, and, therefore, Q = W, or heat has been converted completely into work.

This process, however, involves a change of state of the gas. The volume increases

and the pressure decreases until atmospheric pressure is reached, at which point the

process stops. Therefore, the process of isothermal expansion cannot be used

indefinitely .

2nd law of thermodynamics

What is needed is a series of processes in which a system is brought back

to its initial state, that is, a cycle.

Each of the processes that constitute a cycle involves either the performance of work or

a flow of heat

68 between the system

INTRODUCTION and

TO THE its surroundings

THERMODYNAMICS OF MATERIALS, SIXTH EDITION

temperature t2 engine temperature t1

Work, w

Figure 3.3 Schematic representation of the working of a heat engine.

the symbol QH represent the heat exchanged between the high-temperature reservoir

and the system;

the symbol QL represent the heat exchanged between the low-temperature reservoir and

the system; Rumford in 1798. In the operation of a heat engine, some of the energy that has been

the symboltransferred from a the

W represent high-temperature

work exchangedheat reservoir

between is converted into work,

the system andwith

thethe

surroundings.

remainder ofQthe

All three quantities energy being transferred to a low-temperature heat reservoir. The

H, QL, and W, are expressed as absolute values, that

process is shown schematically in Figure 3.3. Treating the engine as the system, the

is, positiveFirst

numbers only.

Law gives

2nd law of thermodynamics

If QH is larger than QL and if W is done by the system, then the

machine

68 thatINTRODUCTION

causes the TO

system to undergo theOFcycle

THE THERMODYNAMICS is called

MATERIALS, aEDITION

SIXTH heat engine.

temperature t2 engine temperature t1

Work, w

The purpose of a heat engine is to deliver work continuously to the surroundings by

performing the same cycle over and over again.

Rumford in 1798. In the operation of a heat engine, some of the energy that has been

The net work in the cycle is the output, and the heat absorbed from the high-temperature

transferred from a high-temperature heat reservoir is converted into work, with the

reservoir by the

remainder system

of the energy is thetransferred

being input. to a low-temperature heat reservoir. The

process is shown schematically in Figure 3.3. Treating the engine as the system, the

First Law gives

∆U ′ = q2 − q1 − w

Consider the steam engine, which is a typical example of a heat engine. In a steam

2nd law of thermodynamics

The thermal efficiency of the engine, symbolized by η, is defined as

Applying the first law to one complete cycle, remembering that there is no change of

internal energy, we get

2nd law of thermodynamics

Important characteristics of heat-engine cycles are as follows:

1. There is some process or series of processes during which there is an

absorption of heat from an external reservoir at a higher temperature.

2. There is some process or series of processes during which heat is rejected to

an external reservoir at a lower temperature.

2nd law of thermodynamics

from the working substance to the low- temperature reservoir, then there would be

100 percent conversion of heat from the high-temperature reservoir into work.

2nd law of thermodynamics

No heat-engine has ever been developed that converts

the heat extracted from a reservoir at a higher

temperature into work without rejecting some heat to a

reservoir at a lower temperature.

of everyday experience, constitutes the second law of

thermodynamics and has been formulated in several

ways.

"It is impossible by means of inanimate material agency

to derive mechanical effect from any portion of matter by

cooling it below the temperature of the coldest of the

surrounding objects."

2nd law of thermodynamics

mechanics,

which, working in a complete cycle, will produce no effect

other than the

raising of a weight and the cooling of a heat reservoir."

statement Kelvin-Planck statement of the second law,

thus:

It is impossible to construct an engine that, operating in a

cycle, will produce no effect other than the extraction of

heat from a reservoir and the performance of an

equivalent amount of work.

2nd law of thermodynamics

If the second law were not true, it would be possible to propel a ship across

the ocean by extracting heat from the ocean or to run a power plant by extracting heat

from the surrounding air.

Notice that neither of these "impossibilities” violates the first law of thermodynamics.

After all, both the ocean and the surrounding air contain an enormous store of internal

energy, part of which you might hope could be extracted in the form of a flow of heat.

The continuous operation of a machine that creates its own energy and thus violates

the first law is called a perpetual motion machine of the first kind.

The operation of a machine that utilizes the internal energy of only one heat reservoir,

thus violating the second law, is called a perpetual motion machine of the second kind.

2nd law of thermodynamics

HEAT ENGINE

Heat engine is a machine that takes a working substance through a cycle in such a

sequence of processes that some heat is absorbed by the system from a high-

temperature heat reservoir, a smaller amount of heat is rejected to a low-temperature

heat reservoir, and a net amount of work is done by the system on the surroundings.

2nd law of thermodynamics

REFRIGERATOR

Some heat is absorbed by the system from a heat reservoir at a low temperature, a

larger amount of heat is rejected to a heat reservoir at a high temperature, and a net

amount of work is done on the system by the surroundings.

A machine that performs a cycle in this direction is called a refrigerator, and the working

substance (system) is called a refrigerant.

2nd law of thermodynamics

QH represents the amount of heat rejected by the

refrigerant to the high-temperature reservoir;

QL represents the amount of heat absorbed by the

refrigerant from the low-temperature reservoir;

W represents the net work done on the refrigerant by the

surroundings.

in internal energy, and the first law becomes

is larger than the heat extracted from the low-temperature

reservoir by the amount of work done on the refrigerant.

2nd law of thermodynamics

The purpose of a refrigerator is to extract as much heat QL

as possible from the low-temperature reservoir with the

expenditure of as little work W as possible.

temperature reservoir to a higher-temperature reservoir,

because it is a fact of nature that heat does not flow

spontaneously from a lower-temperature reservoir to a

higher-temperature reservoir.

statement of the second law:

effect other than the transfer of heat from a lower-temperature reservoir to a higher-

temperature reservoir.

2nd law of thermodynamics

EQUIVALENCE OF THE KELVIN-PLANCK AND CLAUSIUS STATEMENTS

-K = falsity of the Kelvin-Planck statement;

-C = falsity of the Clausius statement.

Two propositions or statements can be said to be equivalent when the truth of one

implies the truth of the second, and the truth of the second implies the truth of the first.

other, namely,

2nd law of thermodynamics

Thus, in order to demonstrate the equivalence of K and C, falsity of one statement

implies the falsity of the second, and vice-versa

work to transfer QL units of heat from a

low- temperature reservoir to a high-

X temperature reservoir

2nd law of thermodynamics

Suppose that a heat engine also operates between the same two reservoirs in such a

way that the same heat QL is delivered to the low-temperature reservoir

law by itself

constitute a self-contained machine

QH-QL from the high-temperature reservoir and

converts all this heat into work without

producing any change in the low-temperature

reservoir.

2nd law of thermodynamics

converts all this heat into work without

producing any change in the low-

temperature reservoir.

Therefore, the refrigerator and heat engine together constitute a violation of the Kelvin-

Planck statement.

2nd law of thermodynamics

to the low-temperature reservoir

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.

constitute a self-contained machine

This self contained machine transfers heat QL from the low-temperature reservoir to

the high-temperature reservoir without producing any changes elsewhere.

Therefore, the engine and refrigerator together constitute a violation of the Clausius

statement.

2nd law of thermodynamics

During a part of the cycle performed by the working substance in an engine,

some heat is absorbed from a hotter reservoir;

during another part of the cycle, a smaller amount of heat is rejected to a cooler

reservoir.

operate between these two

reservoirs.

some heat is always rejected to the

cooler reservoir, the efficiency of an

actual engine is never 100 percent.

2nd law of thermodynamics

Lets say that we have at our disposal two reservoirs at given temperatures

(1) What is the maximum thermal efficiency that can be achieved by an engine

operating between these two reservoirs?

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.

the temperature drops to that of the low-temperature reservoir, TL .

reversible isothermal process is performed in a direction opposite to process 2 until the

working substance and the surroundings are in their initial states. During this process,

heat QL is rejected to the low-temperature reservoir.

2nd law of thermodynamics

An engine operating in a Carnot cycle is called a Carnot engine.

A Carnot engine operates between two reservoirs in a particularly simple way. All the

absorbed heat enters the system at a constant high temperature, namely, that

of the hotter reservoir.

Also, all the rejected heat leaves the system at a constant low temperature, that of the

cooler reservoir.

Notice that the exchange of heat in the Carnot cycle is unlike the situation for idealized

real engines, which need a series of reservoirs to exchange heat during the constant-

volume or constant-pressure processes in order to achieve reversibility.

process.

Since all four processes are reversible, the Carnot engine is a reversible engine.

2nd law of thermodynamics

EXAMPLES OF CARNOT CYCLES

The simplest example of a Carnot cycle is that of a gas which can be depicted on a PV

diagram.

the point 1.

1. Process 1 to 2, reversible adiabatic compression until

the temperature rises to TH·

any desired point, such as 3, is reached.

temperature drops to TL.

the original state is reached.

2nd law of thermodynamics

For a two-phase system, such as steam and

water, the Carnot cycle has a shape quite

different from a gaseous system.

isobaric vaporization of the liquid at the higher

temperature TH;

isobaric condensation of the vapor at the lower

temperature T L .

Any point between the dashed lines L and V represents a mixture of liquid and vapor.

2nd law of thermodynamics

Starting at the point 1, the four processes in the

Carnot cycle are as follows:

temperature rises to T H .

2. Process 2 to 3, reversible isothermal isobaric vaporization

until any arbitrary point, such as 3, is reached.

3. Process 3 to 4, reversible adiabatic expansion until the

temperature drops to T L.

4. Process 4 to 1, reversible isothermal isobaric

condensation until the initial state is reached.

During the isothermal vaporization 2 to 3, heat QH is absorbed from the hotter reservoir

at TH .

TL .

2nd law of thermodynamics

electrochemical cell (acid battery) on which obeys Curie's law is shown on a H-M

an E-z diagram diagram. Lines 0TH and 0TL represent

The lines marked TH and TL represent isothermal lines at the temperatures

isothermal and constant emf curves at TH and TL , respectively

the two temperatures of the reservoirs.

The point 1 indicates that the cell is

well charged.

2nd law of thermodynamics

The net work done in one cycle by any Carnot engine

can be adjusted to any arbitrary amount by choosing

the position of the point 3

3, we can control the amount of heat QH from the high-

temperature reservoir.

The nature of the working substance determines the thermodynamic coordinates used

to plot a Carnot cycle, as well as the shape of the cycle.

If an engine is to operate between only two reservoirs and still operate in a reversible

cycle, then it must be a Carnot engine.

2nd law of thermodynamics

CARNOT REFRIGERATOR

reversible processes, it may be

performed in either direction.

opposite, it is a refrigeration cycle

The important feature of a Carnot refrigeration cycle, which distinguishes it from any

general reversed engine cycle, is that the quantities QH, QL, and W are numerically

equal to those quantities when the cycle is performed in the opposite direction.

Example, exactly same amount of heat that is absorbed by the Carnot engine from the

high-temperature reservoir is rejected to the high-temperature reservoir when the cycle

is reversed.

2nd law of thermodynamics

CARNOT'S THEOREM AND COROLLARY

No heat engine operating between two given reservoirs can be more efficient than a

Carnot engine operating between the same two reservoirs.

Imagine a Carnot engine R, which is reversible, and any other engine I, which is

irreversible, working between the same two reservoirs and adjusted so that they both

deliver the same amount of work W.

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.

is

which is positive.

is

heat from a low-temperature reservoir to a high-temperature reservoir without work being

done by the surroundings.

2nd law of thermodynamics

All Carnot engines operating between the same two reservoirs have the same efficiency.

Consider two Carnot engines R1 and R2, operating between the same two reservoirs.

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.

operates between two reservoirs, rather than two series of reservoirs.

3. The superior efficiency of the Carnot cycle is due to its absorbing all heat at the

highest temperature and rejecting all heat at the lowest temperature.

the system.

2nd law of thermodynamics

Efficiency of a Carnot cycle is independent of working substance and depends only on

the temperature.

The Carnot engine provides the basis for the thermodynamic temperature scale.

2nd law of thermodynamics

Lets take three Carnot engines operating between three reservoirs with T1 > T3 > T2

2nd law of thermodynamics

For engine RA,

third Carnot engine RC.

Carnot engine RB is absorbed by the third

Carnot engine RC, both engines working

together are equivalent to the first

Carnot engine RA.

Thus, engine RB absorbs the same heat Q1 from the reservoir at T1 that engine RA

absorbs.

So, for engine RB ,

2nd law of thermodynamics

Engine RA rejects heat Q2 to the low-

temperature reservoir, so engine Rc

must also reject heat Q2 to the low-

temperature reservoir. Thus, for engine

Rc,

2nd law of thermodynamics

of two thermodynamic temperatures and is

denoted by T1/T2.

Thus, two temperatures on the thermodynamic scale are to each other as the

absolute values of the heats absorbed and rejected, respectively, by a Carnot

engine operating between reservoirs at these temperatures

of any particular substance

2nd law of thermodynamics

So, the Carnot engine supplies the universality that is lacking in the ideal-gas

temperature scale.

they are independent of any material.

Kelvin was forced to choose a linear function of temperature, because all the scientific

and engineering data had been obtained from the mercury-in-glass thermometer, which

is essentially linear over its useful range.

temperatures vary from 0 to +infinity for ordinary systems.

The advantage of the logarithmic scale is that absolute zero is far removed from the

normal freezing point of water, whereas, on the linear scale, absolute zero is "only" a few

hundred degrees below the ice point.

2nd law of thermodynamics

At first thought, it might seem that the ratio of two Kelvin temperatures

would be impossible to measure, since a Carnot engine is an ideal engine, quite

impossible to construct.

The ratio of two Kelvin temperatures is the ratio of two heats that are transferred

during two isothermal processes bounded by the same two adiabatic curves.

The two adiabatic boundaries may be located experimentally, and the heats

transferred during two isothermal "nearly reversible" processes can be measured with

considerable precision.

As a matter of fact, this is one of the methods used in measuring temperatures below 1K.

2nd law of thermodynamics

To complete the definition of the thermodynamic scale, we assign the arbitrary value of

273.16 K to the temperature of the triple point of water TTP.

For a Carnot engine operating between reservoirs at the temperatures T and TTP, we

have

for a Carnot cycle, just as pressure is the thermometric property for a constant-volume

gas thermometer.

2nd law of thermodynamics

ABSOLUTE ZERO AND CARNOT EFFICIENCY

The smaller the value of Q , the lower the corresponding T. The smallest possible

value of Q is zero, and the corresponding T is absolute zero.

the temperature at which this process takes place is called 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.

diagram

and 4 to 1 at temperature θ2 are represented by

equilateral hyperbolas

2nd law of thermodynamics

For any infinitesimal reversible process of an ideal gas, the first law may be written as

rejected is

2nd law of thermodynamics

Since the process 1 to 2 is adiabatic, we may write, for any infinitesimal change

2nd law of thermodynamics

If θ1 and T1 refer to any temperature, and θ2 and T2 refer to the triple point of

water, then

therefore, numerically equal to the ideal-

gas temperature and, in the proper range,

Since θTP= TTP = 273.16 K, it follows that may be measured with a gas thermometer.

MM209 - Thermodynamics

Instructor : Aswani Yella

2nd law of thermodynamics

mechanics,

which, working in a complete cycle, will produce no effect

other than the

raising of a weight and the cooling of a heat reservoir."

statement Kelvin-Planck statement of the second law,

thus:

It is impossible to construct an engine that, operating in a

cycle, will produce no effect other than the extraction of

heat from a reservoir and the performance of an

equivalent amount of work.

2nd law of thermodynamics

The purpose of a refrigerator is to extract as much heat QL

as possible from the low-temperature reservoir with the

expenditure of as little work W as possible.

temperature reservoir to a higher-temperature reservoir,

because it is a fact of nature that heat does not flow

spontaneously from a lower-temperature reservoir to a

higher-temperature reservoir.

statement of the second law:

effect other than the transfer of heat from a lower-temperature reservoir to a higher-

temperature reservoir.

2nd law of thermodynamics

Lets say that we have at our disposal two reservoirs at given temperatures

(1) What is the maximum thermal efficiency that can be achieved by an engine

operating between these two reservoirs?

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.

operates between two reservoirs, rather than two series of reservoirs.

3. The superior efficiency of the Carnot cycle is due to its absorbing all heat at the

highest temperature and rejecting all heat at the lowest temperature.

the system.

2nd law of thermodynamics

An isothermal process or an adiabatic process is represented by a different curve on

each diagram.

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

corresponding generalized displacement V, L, A, Z, or have been used to indicate

processes of various systems.

2nd law of thermodynamics

Consider a reversible process represented by the smooth curve i to f on the

generalized work diagram.

represent portions of adiabatic processes.

isothermal process, in such a way that the area

under the smooth curve i is equal to the area under

the zigzag sequence of processes, path iabf

2nd law of thermodynamics

From the 1st law

processes ia and bf, we have

change in any manner, it is always possible to find a reversible zigzag path

between the same two states, consisting of an adiabatic process followed by an

isothermal process followed by an adiabatic process, such that the heat transferred

during the isothermal segment is the same as that transferred during the

original process.

2nd law of thermodynamics

Now, consider the smooth closed curve on the generalized work diagram.

a number of adiabatic lines may be drawn,

dividing the cycle into a number of

adjacent strips.

A zigzag closed path may now be drawn, consisting of alternate adiabatic and

isothermal portions, such that the heat transferred during all the isothermal portions is

equal to the heat transferred in the original cycle.

2nd law of thermodynamics

Consider the two isothermal processes ab and cd at the temperature T1 and T2

respectively.

temperature T1, heat Q1 is absorbed,

and the process cd conducted at the

temperature T2, heat Q2 is

rejected.

same adiabatic curves, abed is a

Carnot cycle, and we so we can write

2nd law of thermodynamics

For the sake of simplicity, we have been considering only the absolute values of heat

entering or leaving a system, thus ignoring the sign convention

and regard any Q as an algebraic symbol,

positive for heat absorbed by a system

and negative for heat rejected from a system.

We may then write

Q2 is a negative number.

2nd law of thermodynamics

Since the isothermal curves ef and gh are bounded by the same two adiabatic

curves, efgh is also a Carnot cycle

isothermal curves bounded by the same two

adiabatic curves and if all the equations are

added, then the result obtained is that

Since no heat is transferred during the adiabatic portions of the zigzag cycle,

we may write

where the summation is taken over the entire zigzag cycle consisting of Carnot

cycles, j in number.

2nd law of thermodynamics

Now, imagine the cycle divided into a very large number of strips by

drawing a large number of adiabatic curves close together.

with small isothermal curves, then a

zigzag path may be traced that can

be made to approximate the original cycle

as closely as we want.

become infinitesimal, the ratio dQ/T for an infinitesimal isothermal between

two adjacent adiabatic curves is equal to the ratio dQ/T for the infinitesimal

piece of the original cycle bounded by the same two adiabatic curves.

2nd law of thermodynamics

In the limit, therefore, for any reversible cycle, we can write

signifies that the integration takes place

over the complete cycle, and the letter

R emphasizes the fact that the equation

is true only for a reversible cycle.

statement of the second law.

2nd law of thermodynamics

For every infinitesimal amount of heat that enters a system during an infinitesimal

portion of a reversible process, there is an equation

process is given by

diagram in which T is plotted along the y-axis and S along the x-axis, a so-

called "TS diagram.”

The shape of the curve on the TS diagram is determined by the kind of reversible

process that the system undergoes.

2nd law of thermodynamics

An isothermal process is a horizontal line

In the case of a reversible adiabatic process

and S is constant.

of a system remains constant, or, in other words, the system undergoes an

isentropic process.

2nd law of thermodynamics

Other processes can also be plotted on a TS diagram. For a reversible isobaric

process, the curve has a slope,

Volume, the slope of a reversible isochoric

process is given by

The slopes are independent of the nature of the hydrostatic system, because the

requirement of constant pressure and constant volume eliminated the equation of

state of the ideal gas

2nd law of thermodynamics

Two isothermal and the two adiabatic

processes that make up any Carnot cycle form

a rectangle on a TS diagram, regardless of the

Temperature

nature of the working substance

TS diagram, because of the definition of

entropy

Entropy

representing all the idealized reversible cycles

for various heat engines.

2nd law of thermodynamics

The TS diagram is particularly convenient for

representing all the idealized reversible cycles

for various heat engines.

R1 and a lower portion R2 represents any

reversible engine cycle that is not a

Carnot cycle.

The area under R1 (positive area) is equal to the positive heat Q1 absorbed by

the system, and the area under R2 (negative area) is equal to the negative heat

Q2 rejected by the system.

The 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

calculate its closed integral.

dQ1 to an auxiliary reversible engine R.

reversible heat for the irreversible engine I.

of heat dQ at temperature T that is supplied

to the irreversible engine I.

2nd law of thermodynamics

Engine R rejects a small amount of heat dQ at temperature T that is supplied to

the irreversible engine I.

during an irreversible cycle, so the combined system

of engine R and engine I also performs an

irreversible cycle.

the first law, equals dQ1.

statement of the second law, since the combined system

exchanges heat with a single reservoir.

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.

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,

in differential form for reversible engine R,

2nd law of thermodynamics

Integrating around a cycle,

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

in an initial equilibrium state i, passes

during an irreversible process I to a final

equilibrium state f, and then returns by a

reversible process R to the initial state i,

integral is always zero:

2nd law of thermodynamics

Since entropy is a state function, its closed integral is always zero:

2nd law of thermodynamics

The term reversible adiabatic implies the term isentropic.

dQ = 0 reversible,

Or dQ < 0 irreversible.

reversible. But, irreversible isentropic is not adiabatic dQ < 0 and implies that

heat flows out of the system.

2nd law of thermodynamics

ENTROPY AND THE CRITERION FOR EQUILIBRIUM

Spontaneous process is, irreversible, and the movement of the system from its initial

non-equilibrium state to its final equilibrium state is accompanied by an increase in the

entropy of the system.

The attainment of the equilibrium state coincides with the entropy reaching a maximum

value, and hence, for such systems, entropy can be used as a criterion for determining

the equilibrium state.

equilibrium is attained when the entropy of the system is at maximum, consistent with

the fixed values of U and V.

2nd law of thermodynamics

ENTROPY AND THE CRITERION FOR EQUILIBRIUM

Consider the chemical reaction occurring in anLAW

THE SECOND adiabatic enclosure at constant volume

OF THERMODYNAMICS

A+B=C+D

proceed from left to right as long as the

Entropy

entropy of the system is thereby increased; Equilibrium

or, conversely, starting with C and D, the

reaction will proceed from right to left,

again provided that the entropy of the

system is thereby increased. (A + B) Composition (C + D)

A point is reached along the reaction coordinate

+ D as at which ofthe

a function theentropy of reaction

extent of the the system

A + B has

= C + D at co

its maximum value. energy and volume.

occur spontaneously. This concept will be utilized when we discuss th

gases in Chapter 11.

2nd law of thermodynamics

Suppose one wants to cool an object with a refrigerator

to a desired low temperature, that is, to lower the

temperature of a body of finite mass from the

temperature T1 of its surroundings to any desired low

temperature T2.

at T1 and the body itself is utilized, and, after several

complete cycles have been completed, a

quantity of heat Q has been removed from the body, a

quantity of work W has been supplied to the

refrigerator, and a quantity of heat Q + W has been

rejected to the reservoir

2nd law of thermodynamics

Applying the entropy principle, we obtain

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

follows:

δ q rev dU PdV C V

dS = = + = dT = C V d ln T

T T T T

T2

ΔSV = S2 − S1 = ∫ C V d ln T

T1

follow:

δ q rev 1 1 1 C dT

dS = = [dU + d (PV )] = d (U + PV ) = dH = P = C P d ln T

T T T T T

T2

ΔSP = S2 − S1 = ∫ C p d ln T

T1

2nd law of thermodynamics

Volume Dependence of entropy

We know; δ q rev 1

dS = = [dU + d (PV )]

T T

dU = ⎜⎜ ⎟⎟ dT + ⎜⎜ ⎟⎟ dV

⎝ ∂ T ⎠V ⎝ ∂ V ⎠T

1 ⎛∂U⎞ 1 ⎡⎛ ∂ U ⎞ ⎤

dS = ⎜⎜ ⎟⎟ dT + ⎢⎜⎜ ⎟⎟ + P ⎥ dV

So T ⎝ ∂ T ⎠V T ⎢⎣⎝ ∂ V ⎠T ⎥⎦

Hence

∂ ⎡1 ⎛∂U⎞ ⎤ ∂ ⎡1 ⎛∂U⎞ P ⎤

⎢ ⎜⎜ ⎟⎟ ⎥ = ⎢ ⎜⎜ ⎟⎟ + ⎥

∂ V ⎢⎣ T ⎝ ∂ T ⎠ V ⎥⎦ ∂ T ⎢⎣ T ⎝ ∂ V ⎠T T ⎥⎦ V

T

2nd law of thermodynamics

Volume Dependence of entropy

⎛∂P⎞ ⎛∂U⎞

T ⎜⎜ ⎟⎟ = ⎜⎜ ⎟⎟ + P

⎝ ∂ T ⎠ V ⎝ ∂ V ⎠T

So we can write

1 ⎛∂U⎞ ⎛ ∂P⎞

dS = ⎜⎜ ⎟⎟ dT + ⎜⎜ ⎟⎟ dV

T ⎝ ∂ T ⎠V ⎝ ∂ T ⎠V

And under isothermal condition dT = 0 lead to the following expression:

⎛ ∂P ⎞

dS T = ⎜⎜ ⎟⎟ dV

⎝ ∂ T ⎠V

2nd law of thermodynamics

Volume Dependence of entropy

⎛ ∂P ⎞

dS T = ⎜⎜ ⎟⎟ dV

⎝ ∂ T ⎠V

⎛∂P⎞

In case of gas one can directly integrate the above expression to calculate the ⎜⎜

∂ T

⎟⎟

⎝ ⎠V

change in entropy during a process.

However, in case of solid and liquids, the equation of state is not known and

can also not be determined experimentally. Hence in such cases this partial

differential is required to be expressed in terms of some experimentally

determinable parameters. For this purpose the reciprocity theorem is used to write

the following:

⎛ ∂P⎞ ⎛∂V⎞ ⎛ ∂P ⎞

⎜⎜ ⎟⎟ = − ⎜⎜ ⎟⎟ .⎜⎜ ⎟⎟

⎝ ∂ T ⎠V ⎝ ∂ T ⎠P ⎝ ∂ V ⎠T

2nd law of thermodynamics

Volume Dependence of entropy

• Isobaric coefficient of volumetric thermal expansion of a material (α) is

given as

1 ⎛∂V⎞

α = ⎜⎜ ⎟⎟

V ⎝ ∂ T ⎠P

• Isothermal compressibility of a material (β) is given as

1 ⎛∂V⎞

β = − ⎜⎜ ⎟⎟

V ⎝ ∂ P ⎠T

• So

α

dS = dV

β

Which on integration will yield the change in entropy for a change in volume

from V1 to V2 under isothermal condition

2nd law of thermodynamics

Pressure dependency of entropy

We know: δ q rev 1 P 1

dS = = dU + dV = (dU + P dV )

T T T T

From the definition of the enthalpy, one can get the total differential dH which can

be expressed as

dH = dU + P dV + VdP

1 V

dS = dH − dP

T T

⎛∂H⎞ ⎛∂H⎞

dH = ⎜⎜ ⎟⎟ dT + ⎜⎜ ⎟⎟ dP

⎝ ∂ T ⎠P ⎝ ∂ P ⎠T

2nd law of thermodynamics

Pressure dependency of entropy

After substitution, we get

1 ⎛∂H⎞ ⎡ 1 ⎛ ∂ H ⎞ V⎤

dS = ⎜⎜ ⎟⎟ dT + ⎢ ⎜⎜ ⎟⎟ − ⎥ dP

T ⎝ ∂ T ⎠P ⎢⎣ T ⎝ ∂ P ⎠ T T ⎥⎦

The equation is an exact differential because entropy being function of state.

Therefore,

∂ ⎡1 ⎛∂H⎞ ⎤ ∂ ⎡1 ⎛ ∂ H ⎞ V⎤

⎢ ⎜⎜ ⎟⎟ ⎥ = ⎢ ⎜⎜ ⎟⎟ − ⎥

∂ P ⎢⎣ T ⎝ ∂ T ⎠ P ⎥⎦ T ∂ T ⎢⎣ T ⎝ ∂ P ⎠ T T ⎥⎦ P

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:

⎜⎜ ⎟⎟ = T ⎜⎜ ⎟⎟ − P ⎜⎜ ⎟⎟ = V − T ⎜⎜ ⎟⎟

⎝ ∂ P ⎠T ⎝ ∂ T ⎠P

⎝ ∂ V ⎠T ⎝ ∂ T ⎠V

⎛ ∂P⎞ ⎛∂V⎞ ⎛ ∂P ⎞

⎜⎜ ⎟⎟ = − ⎜⎜ ⎟⎟ .⎜⎜ ⎟⎟

⎝ ∂ T ⎠V ⎝ ∂ T ⎠P ⎝ ∂ V ⎠T

1 ⎛∂V⎞ 1 ⎛∂V⎞

α = ⎜⎜ ⎟⎟ β = − ⎜⎜ ⎟⎟

V ⎝ ∂ T ⎠P V ⎝ ∂ P ⎠T

2nd law of thermodynamics

• We know the following expression

⎛ ∂U ⎞ ⎛ ∂V ⎞ ⎛ ∂V ⎞ ⎛ ∂ V ⎞ ⎡⎛ ∂ U ⎞ ⎤

C P − CV = ⎜⎜ ⎟⎟ ⎜⎜ ⎟⎟ + P ⎜⎜ ⎟⎟ = ⎜⎜ ⎟⎟ ⎢⎜⎜ ⎟⎟ + P⎥

⎝ ∂ V ⎠T ⎝ ∂T ⎠P ⎝ ∂ T ⎠ P ⎝ ∂ T ⎠ P ⎢⎣⎝ ∂ V ⎠T ⎥⎦

⎛∂U⎞

• Elimination of from the above equation

⎜⎜ ⎟⎟

⎝ ∂ V ⎠T

leads to the relation

⎛ ∂P⎞ ⎛ ∂V ⎞

C P − C V = T ⎜⎜ ⎟⎟ ⎜⎜ ⎟⎟

⎝ ∂ T ⎠V ⎝ ∂ T ⎠P

α2 V T

• Or CP − CV =

β

MM209 - Thermodynamics

Instructor : Aswani Yella

2nd law of thermodynamics

mechanics,

which, working in a complete cycle, will produce no effect

other than the

raising of a weight and the cooling of a heat reservoir."

statement Kelvin-Planck statement of the second law,

thus:

It is impossible to construct an engine that, operating in a

cycle, will produce no effect other than the extraction of

heat from a reservoir and the performance of an

equivalent amount of work.

2nd law of thermodynamics

The purpose of a refrigerator is to extract as much heat QL

as possible from the low-temperature reservoir with the

expenditure of as little work W as possible.

temperature reservoir to a higher-temperature reservoir,

because it is a fact of nature that heat does not flow

spontaneously from a lower-temperature reservoir to a

higher-temperature reservoir.

statement of the second law:

effect other than the transfer of heat from a lower-temperature reservoir to a higher-

temperature reservoir.

2nd law of thermodynamics

Lets say that we have at our disposal two reservoirs at given temperatures

(1) What is the maximum thermal efficiency that can be achieved by an engine

operating between these two reservoirs?

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.

operates between two reservoirs, rather than two series of reservoirs.

3. The superior efficiency of the Carnot cycle is due to its absorbing all heat at the

highest temperature and rejecting all heat at the lowest temperature.

the system.

2nd law of thermodynamics

An isothermal process or an adiabatic process is represented by a different curve on

each diagram.

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

corresponding generalized displacement V, L, A, Z, or have been used to indicate

processes of various systems.

2nd law of thermodynamics

Consider a reversible process represented by the smooth curve i to f on the

generalized work diagram.

represent portions of adiabatic processes.

isothermal process, in such a way that the area

under the smooth curve i is equal to the area under

the zigzag sequence of processes, path iabf

2nd law of thermodynamics

From the 1st law

processes ia and bf, we have

change in any manner, it is always possible to find a reversible zigzag path

between the same two states, consisting of an adiabatic process followed by an

isothermal process followed by an adiabatic process, such that the heat transferred

during the isothermal segment is the same as that transferred during the

original process.

2nd law of thermodynamics

Now, consider the smooth closed curve on the generalized work diagram.

a number of adiabatic lines may be drawn,

dividing the cycle into a number of

adjacent strips.

A zigzag closed path may now be drawn, consisting of alternate adiabatic and

isothermal portions, such that the heat transferred during all the isothermal portions is

equal to the heat transferred in the original cycle.

2nd law of thermodynamics

Consider the two isothermal processes ab and cd at the temperature T1 and T2

respectively.

temperature T1, heat Q1 is absorbed,

and the process cd conducted at the

temperature T2, heat Q2 is

rejected.

same adiabatic curves, abed is a

Carnot cycle, and we so we can write

2nd law of thermodynamics

For the sake of simplicity, we have been considering only the absolute values of heat

entering or leaving a system, thus ignoring the sign convention

and regard any Q as an algebraic symbol,

positive for heat absorbed by a system

and negative for heat rejected from a system.

We may then write

Q2 is a negative number.

2nd law of thermodynamics

Since the isothermal curves ef and gh are bounded by the same two adiabatic

curves, efgh is also a Carnot cycle

isothermal curves bounded by the same two

adiabatic curves and if all the equations are

added, then the result obtained is that

Since no heat is transferred during the adiabatic portions of the zigzag cycle,

we may write

where the summation is taken over the entire zigzag cycle consisting of Carnot

cycles, j in number.

2nd law of thermodynamics

Now, imagine the cycle divided into a very large number of strips by

drawing a large number of adiabatic curves close together.

with small isothermal curves, then a

zigzag path may be traced that can

be made to approximate the original cycle

as closely as we want.

become infinitesimal, the ratio dQ/T for an infinitesimal isothermal between

two adjacent adiabatic curves is equal to the ratio dQ/T for the infinitesimal

piece of the original cycle bounded by the same two adiabatic curves.

2nd law of thermodynamics

In the limit, therefore, for any reversible cycle, we can write

signifies that the integration takes place

over the complete cycle, and the letter

R emphasizes the fact that the equation

is true only for a reversible cycle.

statement of the second law.

2nd law of thermodynamics

For every infinitesimal amount of heat that enters a system during an infinitesimal

portion of a reversible process, there is an equation

process is given by

diagram in which T is plotted along the y-axis and S along the x-axis, a so-

called "TS diagram.”

The shape of the curve on the TS diagram is determined by the kind of reversible

process that the system undergoes.

2nd law of thermodynamics

An isothermal process is a horizontal line

In the case of a reversible adiabatic process

and S is constant.

of a system remains constant, or, in other words, the system undergoes an

isentropic process.

2nd law of thermodynamics

Other processes can also be plotted on a TS diagram. For a reversible isobaric

process, the curve has a slope,

Volume, the slope of a reversible isochoric

process is given by

The slopes are independent of the nature of the hydrostatic system, because the

requirement of constant pressure and constant volume eliminated the equation of

state of the ideal gas

2nd law of thermodynamics

Two isothermal and the two adiabatic

processes that make up any Carnot cycle form

a rectangle on a TS diagram, regardless of the

Temperature

nature of the working substance

TS diagram, because of the definition of

entropy

Entropy

representing all the idealized reversible cycles

for various heat engines.

2nd law of thermodynamics

The TS diagram is particularly convenient for

representing all the idealized reversible cycles

for various heat engines.

R1 and a lower portion R2 represents any

reversible engine cycle that is not a

Carnot cycle.

The area under R1 (positive area) is equal to the positive heat Q1 absorbed by

the system, and the area under R2 (negative area) is equal to the negative heat

Q2 rejected by the system.

The 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

calculate its closed integral.

dQ1 to an auxiliary reversible engine R.

reversible heat for the irreversible engine I.

of heat dQ at temperature T that is supplied

to the irreversible engine I.

2nd law of thermodynamics

Engine R rejects a small amount of heat dQ at temperature T that is supplied to

the irreversible engine I.

during an irreversible cycle, so the combined system

of engine R and engine I also performs an

irreversible cycle.

the first law, equals dQ1.

statement of the second law, since the combined system

exchanges heat with a single reservoir.

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.

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,

in differential form for reversible engine R,

2nd law of thermodynamics

Integrating around a cycle,

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

in an initial equilibrium state i, passes

during an irreversible process I to a final

equilibrium state f, and then returns by a

reversible process R to the initial state i,

integral is always zero:

2nd law of thermodynamics

Since entropy is a state function, its closed integral is always zero:

2nd law of thermodynamics

The term reversible adiabatic implies the term isentropic.

dQ = 0 reversible,

Or dQ < 0 irreversible.

reversible. But, irreversible isentropic is not adiabatic dQ < 0 and implies that

heat flows out of the system.

2nd law of thermodynamics

ENTROPY AND THE CRITERION FOR EQUILIBRIUM

Spontaneous process is, irreversible, and the movement of the system from its initial

non-equilibrium state to its final equilibrium state is accompanied by an increase in the

entropy of the system.

The attainment of the equilibrium state coincides with the entropy reaching a maximum

value, and hence, for such systems, entropy can be used as a criterion for determining

the equilibrium state.

equilibrium is attained when the entropy of the system is at maximum, consistent with

the fixed values of U and V.

2nd law of thermodynamics

ENTROPY AND THE CRITERION FOR EQUILIBRIUM

Consider the chemical reaction occurring in anLAW

THE SECOND adiabatic enclosure at constant volume

OF THERMODYNAMICS

A+B=C+D

proceed from left to right as long as the

Entropy

entropy of the system is thereby increased; Equilibrium

or, conversely, starting with C and D, the

reaction will proceed from right to left,

again provided that the entropy of the

system is thereby increased. (A + B) Composition (C + D)

A point is reached along the reaction coordinate

+ D as at which ofthe

a function theentropy of reaction

extent of the the system

A + B has

= C + D at co

its maximum value. energy and volume.

occur spontaneously. This concept will be utilized when we discuss th

gases in Chapter 11.

2nd law of thermodynamics

Suppose one wants to cool an object with a refrigerator

to a desired low temperature, that is, to lower the

temperature of a body of finite mass from the

temperature T1 of its surroundings to any desired low

temperature T2.

at T1 and the body itself is utilized, and, after several

complete cycles have been completed, a

quantity of heat Q has been removed from the body, a

quantity of work W has been supplied to the

refrigerator, and a quantity of heat Q + W has been

rejected to the reservoir

2nd law of thermodynamics

Applying the entropy principle, we obtain

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

follows:

δ q rev dU PdV C V

dS = = + = dT = C V d ln T

T T T T

T2

ΔSV = S2 − S1 = ∫ C V d ln T

T1

follow:

δ q rev 1 1 1 C dT

dS = = [dU + d (PV )] = d (U + PV ) = dH = P = C P d ln T

T T T T T

T2

ΔSP = S2 − S1 = ∫ C p d ln T

T1

2nd law of thermodynamics

Volume Dependence of entropy

We know; δ q rev 1

dS = = [dU + d (PV )]

T T

dU = ⎜⎜ ⎟⎟ dT + ⎜⎜ ⎟⎟ dV

⎝ ∂ T ⎠V ⎝ ∂ V ⎠T

1 ⎛∂U⎞ 1 ⎡⎛ ∂ U ⎞ ⎤

dS = ⎜⎜ ⎟⎟ dT + ⎢⎜⎜ ⎟⎟ + P ⎥ dV

So T ⎝ ∂ T ⎠V T ⎢⎣⎝ ∂ V ⎠T ⎥⎦

Hence

∂ ⎡1 ⎛∂U⎞ ⎤ ∂ ⎡1 ⎛∂U⎞ P ⎤

⎢ ⎜⎜ ⎟⎟ ⎥ = ⎢ ⎜⎜ ⎟⎟ + ⎥

∂ V ⎢⎣ T ⎝ ∂ T ⎠ V ⎥⎦ ∂ T ⎢⎣ T ⎝ ∂ V ⎠T T ⎥⎦ V

T

2nd law of thermodynamics

Volume Dependence of entropy

⎛∂P⎞ ⎛∂U⎞

T ⎜⎜ ⎟⎟ = ⎜⎜ ⎟⎟ + P

⎝ ∂ T ⎠ V ⎝ ∂ V ⎠T

So we can write

1 ⎛∂U⎞ ⎛ ∂P⎞

dS = ⎜⎜ ⎟⎟ dT + ⎜⎜ ⎟⎟ dV

T ⎝ ∂ T ⎠V ⎝ ∂ T ⎠V

And under isothermal condition dT = 0 lead to the following expression:

⎛ ∂P ⎞

dS T = ⎜⎜ ⎟⎟ dV

⎝ ∂ T ⎠V

2nd law of thermodynamics

Volume Dependence of entropy

⎛ ∂P ⎞

dS T = ⎜⎜ ⎟⎟ dV

⎝ ∂ T ⎠V

⎛∂P⎞

In case of gas one can directly integrate the above expression to calculate the ⎜⎜

∂ T

⎟⎟

⎝ ⎠V

change in entropy during a process.

However, in case of solid and liquids, the equation of state is not known and

can also not be determined experimentally. Hence in such cases this partial

differential is required to be expressed in terms of some experimentally

determinable parameters. For this purpose the reciprocity theorem is used to write

the following:

⎛ ∂P⎞ ⎛∂V⎞ ⎛ ∂P ⎞

⎜⎜ ⎟⎟ = − ⎜⎜ ⎟⎟ .⎜⎜ ⎟⎟

⎝ ∂ T ⎠V ⎝ ∂ T ⎠P ⎝ ∂ V ⎠T

2nd law of thermodynamics

Volume Dependence of entropy

• Isobaric coefficient of volumetric thermal expansion of a material (α) is

given as

1 ⎛∂V⎞

α = ⎜⎜ ⎟⎟

V ⎝ ∂ T ⎠P

• Isothermal compressibility of a material (β) is given as

1 ⎛∂V⎞

β = − ⎜⎜ ⎟⎟

V ⎝ ∂ P ⎠T

• So

α

dS = dV

β

Which on integration will yield the change in entropy for a change in volume

from V1 to V2 under isothermal condition

2nd law of thermodynamics

Pressure dependency of entropy

We know: δ q rev 1 P 1

dS = = dU + dV = (dU + P dV )

T T T T

From the definition of the enthalpy, one can get the total differential dH which can

be expressed as

dH = dU + P dV + VdP

1 V

dS = dH − dP

T T

⎛∂H⎞ ⎛∂H⎞

dH = ⎜⎜ ⎟⎟ dT + ⎜⎜ ⎟⎟ dP

⎝ ∂ T ⎠P ⎝ ∂ P ⎠T

2nd law of thermodynamics

Pressure dependency of entropy

After substitution, we get

1 ⎛∂H⎞ ⎡ 1 ⎛ ∂ H ⎞ V⎤

dS = ⎜⎜ ⎟⎟ dT + ⎢ ⎜⎜ ⎟⎟ − ⎥ dP

T ⎝ ∂ T ⎠P ⎢⎣ T ⎝ ∂ P ⎠ T T ⎥⎦

The equation is an exact differential because entropy being function of state.

Therefore,

∂ ⎡1 ⎛∂H⎞ ⎤ ∂ ⎡1 ⎛ ∂ H ⎞ V⎤

⎢ ⎜⎜ ⎟⎟ ⎥ = ⎢ ⎜⎜ ⎟⎟ − ⎥

∂ P ⎢⎣ T ⎝ ∂ T ⎠ P ⎥⎦ T ∂ T ⎢⎣ T ⎝ ∂ P ⎠ T T ⎥⎦ P

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:

⎜⎜ ⎟⎟ = T ⎜⎜ ⎟⎟ − P ⎜⎜ ⎟⎟ = V − T ⎜⎜ ⎟⎟

⎝ ∂ P ⎠T ⎝ ∂ T ⎠P

⎝ ∂ V ⎠T ⎝ ∂ T ⎠V

⎛ ∂P⎞ ⎛∂V⎞ ⎛ ∂P ⎞

⎜⎜ ⎟⎟ = − ⎜⎜ ⎟⎟ .⎜⎜ ⎟⎟

⎝ ∂ T ⎠V ⎝ ∂ T ⎠P ⎝ ∂ V ⎠T

1 ⎛∂V⎞ 1 ⎛∂V⎞

α = ⎜⎜ ⎟⎟ β = − ⎜⎜ ⎟⎟

V ⎝ ∂ T ⎠P V ⎝ ∂ P ⎠T

2nd law of thermodynamics

• We know the following expression

⎛ ∂U ⎞ ⎛ ∂V ⎞ ⎛ ∂V ⎞ ⎛ ∂ V ⎞ ⎡⎛ ∂ U ⎞ ⎤

C P − CV = ⎜⎜ ⎟⎟ ⎜⎜ ⎟⎟ + P ⎜⎜ ⎟⎟ = ⎜⎜ ⎟⎟ ⎢⎜⎜ ⎟⎟ + P⎥

⎝ ∂ V ⎠T ⎝ ∂T ⎠P ⎝ ∂ T ⎠ P ⎝ ∂ T ⎠ P ⎢⎣⎝ ∂ V ⎠T ⎥⎦

⎛∂U⎞

• Elimination of from the above equation

⎜⎜ ⎟⎟

⎝ ∂ V ⎠T

leads to the relation

⎛ ∂P⎞ ⎛ ∂V ⎞

C P − C V = T ⎜⎜ ⎟⎟ ⎜⎜ ⎟⎟

⎝ ∂ T ⎠V ⎝ ∂ T ⎠P

α2 V T

• Or CP − CV =

β

MM209 - Thermodynamics

Instructor : Aswani Yella

2nd law of thermodynamics

Combined statement of

first and second law

• If a system is capable of doing only mechanical work the first law equation can be put as:

dU = δq – P dV. It is not exact differential. Holds true for the reversible processes.

• The second law for the reversible process gives

dS = δq rev / T or δq = T dS

• The two laws therefore can lead to

dU = TdS – P dV or TdS = dU + PdV

This is the combined statement of first and second law.

It includes only those terms which are state functions only and

hence is exact differential equation.

2nd law of thermodynamics

• For irreversible process second law gives

dS > 0

Or therefore, TdS > dU + PdV

dS < 0

Or therefore TdS < dU + P dV

Thermodynamic Potentials

• A system by itself, in isolated state or in contact with

surrounding shall stay in equilibrium unless acted

upon by some constraints.

equilibrium or as a result of external constraint, there

must be a driving force making the system move from

within itself or under the applied constraints.

potential driving the system to change to a new state.

Thermodynamic Potentials

• Is this driving force or potential the same under all conditions of the system or it

varies from condition to condition of the system ?

• Heat flows from higher to lower temperature. The flow is possible due to higher

thermal potential.

• Also higher electrical voltage is driving the electrons under the influence of

electrical potential as voltage.

Thermodynamic Potentials

process to take place?

• It is easy to imagine that a system with higher associated energy will be relatively

unstable as compared to the one having lower energy.

• In other words, when a natural changes take occurs the system moves from higher to

lower energy levels or moves from higher to lower thermodynamic potentials.

• It also means that the energy is a potential driving the system for change to occur.

• It also means that for equilibrium to exist the potential of all the systems or sub-systems

within it must be at the same potential.

Thermodynamic Potentials

• So far the internal energy, enthalpy and entropy have been evolved as

energy parameters but it is not yet known as to whether these act as

potential in driving a particular process?

The Driving Force

of a Chemical Reaction

• Why does a chemical reaction take place?

• It was believed that the energy change accompanying a

reaction can be measured directly by the enthalpy

change at constant pressure, or change in intrinsic

energy (ΔU) at constant volume.

• The reasoning behind this would be apparent – if a

system losses energy as a result of a chemical reaction,

that reaction will take place spontaneously – and the

greater the quantity of heat lost, the greater the driving

force behind the reaction.

The Driving Force

of a Chemical Reaction (cont.)

• C (s)+ O2 (g) = CO2(g) with evolution of heat energy, i.e.

ΔH 0 = −94050 cal/mol which happens to be a driving force in this case.

298

3FeO(s) + 2 Al (l) = 2Fe(l) + Al2O3(s)

Both have negative heats of reaction at 16000C and both take place

spontaneously

ZnO(s) + C(s) = Zn(g) + CO (g)

0 0

Δ H 1373 = +83200 and Δ H 298 = +56800

• This reaction will not take place at 250C but if the system is heated to

11000C, carbon will reduce zinc oxide to produce zinc metal.

The Driving Force

of a Chemical Reaction (cont.)

• we cannot use heats of formation as a criterion of their

tendency to take place. We must therefore search for a

more consistent rule for the driving force of a reaction.

• Consider the reaction: ZnO(s) + C(s) = Zn(g) + CO (g)

• At 11000C, i.e above the boiling point of Zn (9070C),

the reaction will take place between phases indicated

above. At 250C, zinc is a solid (melting point 419.60C)

so that the reaction is

ZnO(s) + C(s) = Zn (s) + CO (g)

The Driving Force

of a Chemical Reaction (cont.)

• The most obvious difference in these reactions apart

from their temperature, is the difference in the physical

state, means a difference in the state of order of a

system and consequently in the entropy of the system.

because at 11000C two molecules of gas are being

produced from two solid molecules whereas at 250C

two solid moles only produce one gaseous mole.

The Driving Force

of a Chemical Reaction (cont.)

• A solid to gas transformation means a comparatively large entropy increase

and the following figures for the reduction of ZnO by C:

ΔS298 = 46 cal / mol deg and ΔS1373 = 68 cal / mol deg

• Why not use entropy change of a reaction as a measure of the driving force

behind a chemical reaction?

• The idea is immediately contradicted if we consider the formation of the

oxide of any metal:

1

Fe(s ) + O 2 (g ) = FeO (s ) , ΔS0298 = - 17 cal / deg mol

2

• We know that this reaction is spontaneous – an oxide film forms readily on

iron at room temperature. Thus a positive entropy change is not the

criterion of a chemical reaction.

Thermodynamic Potentials

• So far the internal energy, enthalpy and entropy have been evolved as

energy parameters but it is not yet known as to whether these act as

potential in driving a particular process?

• For a natural process the system moves from lower to a higher entropy

level hence entropy can not be considered as a driving force.

the process towards equilibrium if already at higher levels ?

Thermodynamic Potentials

• Can internal energy and enthalpy qualify as potentials capable of driving the process

towards equilibrium if already at higher levels ?

• If internal energy and enthalpy are potential terms then changes in them will have to be

zero at equilibrium and these will have to decrease for natural changes and increase for

unnatural changes.

• Let us therefore see if criteria can be evolved mathematically to evaluate what constitute

as thermodynamic potential and if so under what conditions?

Thermodynamic Potentials

Potentials under constant volume

and constant entropy conditions

dV = 0 and dS = 0

i) TdS > dU + P dV for natural process

So under above condition we can write

dU < 0

ii) TdS = dU + P dV for the equilibrium process

So under above conditions we can write

dU = 0

iii) TdS < dU + P dV for unnatural process

So under above conditions we can write

dU > 0

Thermodynamic Potentials

• As internal energy decreases for natural process, remains same at equilibrium

and increases for unnatural process thus fully qualifies to be called as

thermodynamic potential under the conditions of constant volume and entropy.

• As a corollary, the internal energy must be the function of entropy and volume

can be expressed:

U = F (S, V)

Total differential of internal energy is given by

⎛∂U⎞ ⎛∂U⎞

dU = ⎜⎜ ⎟⎟ dS + ⎜⎜ ⎟⎟ dV

⎝ ∂ S ⎠V ⎝ ∂ V ⎠S

Thermodynamic Potentials

dU = ⎜⎜ ⎟⎟ dS + ⎜⎜ ⎟⎟ dV

⎝ ∂ S ⎠V ⎝ ∂ V ⎠S

• On comparison this leads to

⎛∂U⎞ ⎛∂U⎞

• ⎜⎜ ⎟⎟ = T and ⎜⎜ ⎟⎟ = − P

⎝ ∂ S ⎠V ⎝ ∂ V ⎠S

thereby describing the system fully.

• By describing U as a function of any other two variables, it is not possible

to describe the system fully.

Thermodynamic Potentials

Potentials under constant pressure

and constant entropy conditions

dP = 0 and dS = 0

i) TdS > dU + P dV for natural process

So under above condition we can write

dU + d (PV ) < 0

Or d (U + P V) < 0

Or dH < 0

ii) TdS = dU + P dV for the equilibrium process

So under above conditions we can write

dU + d (PV ) = 0

Or dH = 0

Thermodynamic Potentials

iii) TdS < dU + P dV for unnatural process

So under above conditions we can write

dU + d (PV ) > 0

Or dH > 0

So on the whole dH > = < 0 for unnatural, equilibrium

and natural processes as the case may be.

a potential term under constant pressure and entropy

conditions.

Thermodynamic Potentials

• Enthalpy can therefore be described mathematically as: H = F (P, S)

• Total differential of enthalpy can be written as

⎛∂H⎞ ⎛∂H⎞

dH = ⎜⎜ ⎟⎟ dS + ⎜⎜ ⎟⎟ dP

⎝ ∂ S ⎠P ⎝ ∂ P ⎠S

• Also by definition: dH = d (U + P V)

• = dU + P dV + V dP

• = T dS + V dP

• On comparison we get

⎛∂H⎞ ⎛∂H⎞

⎜⎜ ⎟⎟ = T and ⎜⎜ ⎟⎟ = V

⎝ ∂ S ⎠P ⎝ ∂ P ⎠S

Thermodynamic Potentials

and constant temperature conditions

dV = 0 and dT = 0

So under above condition we can write

dU - TdS < 0

Or d ( U – T S) < 0

Let us define new mathematical term

A=U–TS

then dA < 0

Thermodynamic Potentials

ii) TdS = dU + P dV for the equilibrium process

So under above conditions we can write

d ( U – T S) = 0

Or dA = 0

iii) TdS < dU + P dV for the unnatural process

So under above conditions we can write

d ( U – T S) > 0

Or dA > 0

The newly defined function qualifies for being referred as a

potential term under constant volume and temperature

conditions

Thermodynamic Potentials

A being the function of all state variables A also

must be state function. Expressing as before

A = F (V, T)

⎛∂A⎞ ⎛∂A⎞

Total differential of A dA = ⎜⎜ ⎟⎟ dT + ⎜⎜ ⎟⎟ dV

⎝ ∂ T ⎠V ⎝ ∂ V ⎠T

• Now A=U–TS

dA = dU – TdS – S dT

And since, TdS = dU + P dV

Therefore dA = - S dT – P dV

On comparison we get

⎛∂A⎞ ⎛∂A⎞

⎜⎜ ⎟⎟ = − S and ⎜⎜ ⎟⎟ = − P

⎝ ∂ T ⎠V ⎝ ∂ V ⎠T

Thermodynamic Potentials

This function A was first defined by Helmholtz and

therefore is known as Helmholtz free energy.

We know dA = dU – T dS

And for reversible process qrev = T dS

An therefore qrev = dU – dA

From the First law dU = qrev – W

And hence qrev = dU + W

Comparing the two equations for qrev we get

- dA = W

Or dA = - W

That the change in Helmholtz free energy in a process is equal

to the amount of work done by the system on the surrounding

or is equal to the amount of work the system is capable of doing.

Thermodynamic Potentials

Potentials under constant pressure

and constant temperature conditions

These are by far the most commonly adopted conditions in chemical and

metallurgical engineering practices. It means

dP = 0 and dT = 0

So under above condition we can write

dU + d (P V) - TdS < 0

Or d ( U + P V– T S) < 0

Let us define new mathematical term

G = U + P V– T S

then dG < 0

Thermodynamic Potentials

ii) TdS = dU + P dV for the equilibrium process

So under above conditions we can write

d ( U + P V– T S) = 0

Or dG = 0

iii) TdS < dU + P dV for the unnatural process

So under above conditions we can write

d ( U + P V– T S) > 0

Or dG > 0

called as a potential term under constant pressure

and temperature conditions

Thermodynamic Potentials

The function G is referred to as Gibbs free energy.

Now G=U+PV–TS

And H=U+PV

Then G=H–TS

Or Δ G = Δ H – T ΔS for a finite change

Or dG = dH – T dS – SdT in differential form

At constant pressure dP = 0 and dH = q = TdS

And hence dG = - SdT

Or

⎛ dG ⎞

⎜⎜ ⎟⎟ = − S

⎝ d T ⎠P

Thermodynamic Potentials

Again dG = dH – T dS – SdT

On putting dH = dU + P dV + V dP

dG = dU + P dV + VdP – T dS – SdT

Putting in this dU + P dV = T dS

dG = T dS + V dP – T dS – S dT

= V dP – S dT

At constant temperature when dT = 0 ; dG = V dP

Or

⎛ dG ⎞

⎜⎜ ⎟⎟ = V

⎝ d P ⎠T

Thermodynamic Potentials

Since G is a state function any change in G can be

represented as

ΔG = Δ U – T ΔS + Δ (P V)

= - Wrev + Δ (P V)

The change of Gibbs free energy during a process is

equal and opposite in sign to the net reversible work

obtainable from the process occurring under

isothermal condition when corrected for change in

volume under isobaric condition.

Thermodynamic Potentials

If the state of a system is described by a func>on of two variables f(x, y) , which sa>sﬁes the

equa>on

df = udx + vdy,

and we wish to change the descrip>on to one involving a new func>on g(u, y) , sa>sfying a

similar equa>on in terms of du and dy, then it is necessary to deﬁne the Legendre transform

g(u,y) as

Thermodynamic Potentials

Consider the ﬁrst law of thermodynamics for a hydrosta>c system with heat expressed in terms

of temperature and entropy,

involving changes in volume and entropy. For other situa>ons, it is easier to work with diﬀerent

variables involving diﬀerent func>ons.

It is important to realize that no informa>on is lost in the transforma>on from one characteris>c

func>on to another. The gain is a new func>on expressed in thermodynamic coordinates

amenable to the experimental situa>on at hand.

Thermodynamic Potentials

Important thermodynamic relations

For closed and isolated systems have fixed mass and composition and the reversible

work is done against pressure.

dU = T dS - PdV

dH = T dS + V dP

dA = - S dT – P dV

dG = - S dT + V dP

These diﬀeren>al equa>ons expressing U in terms of V and S, H in terms of P and S, and so forth,

form a complete set of func>ons, based on successive Legendre transforma>ons of the four

thermodynamic variables P, V, T, and S for a hydrosta>c system.

The characteris>c func>ons U(V, S), H(P, S), A(V, T), and G(P, T) are known as thermodynamic

poten0al func0ons because they have the property that if the func>ons are expressed in terms

of the appropriate thermodynamic variables, then all the thermodynamic proper>es of a system

can be calculated by diﬀeren>a>on only.

Thermodynamic Potentials

Important thermodynamic relations

For other simple systems, such as wires, surfaces, baWeries, electrets, or paramagnets, the

thermodynamic coordinates of pressure and volume are replaced by appropriate conjugate

variables

Extensive quan>>es simply replace volume, whereas intensive quan>>es replace nega>ve

pressure.

follows

Thermodynamic Potentials

(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

constant the Gibbs free energy criteria is employed in

chemical and metallurgical processes. However, in other

areas, other criteria are also employed.

The Driving Force

of a Chemical Reaction (cont.)

• C (s)+ O2 (g) = CO2(g) with evolution of heat energy, i.e.

ΔH 0 = −94050 cal/mol which happens to be a driving force in this case.

298

3FeO(s) + 2 Al (l) = 2Fe(l) + Al2O3(s)

Both have negative heats of reaction at 16000C and both take place

spontaneously

ZnO(s) + C(s) = Zn(g) + CO (g)

0 0

Δ H 1373 = +83200 and Δ H 298 = +56800

• This reaction will not take place at 250C but if the system is heated to

11000C, carbon will reduce zinc oxide to produce zinc metal.

The Driving Force

of a Chemical Reaction (cont.)

• A solid to gas transformation means a comparatively large entropy increase

and the following figures for the reduction of ZnO by C:

ΔS298 = 46 cal / mol deg and ΔS1373 = 68 cal / mol deg

• Why not use entropy change of a reaction as a measure of the driving force

behind a chemical reaction?

• The idea is immediately contradicted if we consider the formation of the

oxide of any metal:

1

Fe(s ) + O 2 (g ) = FeO (s ) , ΔS0298 = - 17 cal / deg mol

2

• We know that this reaction is spontaneous – an oxide film forms readily on

iron at room temperature. Thus a positive entropy change is not the

criterion of a chemical reaction.

The Driving Force

of a Chemical Reaction (cont.)

• The Second Law of thermodynamics states that a

spontaneous process is always accompanied by an

increase in entropy of the system and its surroundings.

• The surroundings receive a quantity of heat - ΔH at

constant temperature and pressure

− ΔH

∴entropy increase of the surroundings =

T

• If ΔS is the entropy change of the system, total entropy

change of the system and surroundings = ΔS – ΔH

T

T

TΔS - ΔH

= + ve

T

The Driving Force

of a Chemical Reaction (cont.)

• we can say that (ΔH – T ΔS) must always be –ve for a reaction to proceed

spontaneously in order that the total entropy change of the system and

surroundings can be +ve, when the reaction proceeds.

• We should examine the factor (ΔH – T ΔS) for the above three reactions in

question. For the reduction of ZnO by C at 250C

ΔH 298 - TΔS298 = 56800 -298(46) = +43100 cal / deg mol

• The reaction cannot proceed because this factor is +ve, and the total entropy

change of the system and its surroundings is –ve

at 11000 C ΔH1373 - TΔS1373 = 83300 -1373(68) = - 10200 cal

• This is negative so that the reaction will take place spontaneously at 11000C.

This explains why zinc oxide smelting must be carried out at temperature of the

order of 11000C in order that reduction of the oxide by carbon can proceed.

The Driving Force

of a Chemical Reaction (cont.)

• For the oxidation of iron at 250C

ΔH 298 − TΔS 298 = − 63200 − 298(− 17 )= − 57140 cal.

spontaneously at 250C.

Consistent Rule

• The driving force of a reaction can be calculated as (ΔH

- TΔS); the more negative this factor, the greater the

driving force and if the factor is +ve, the reaction will

not proceed spontaneously.

• ΔG = ΔH - TΔS called Gibbs Free energy

The Driving Force

of a Chemical Reaction (cont.)

• It is the maximum work available from a system at constant

pressure other than that due to a volume change. Most

metallurgical processes work at constant pressure.

factor (ΔH-TΔS), so that ΔG is a measure of the driving

force behind a chemical reaction. For a spontaneous

change in the system, ΔG must be negative, the more

negative, the greater the driving force.

Chemical Potential

• The general equation for the free energy change of a system with

temperature and pressure dG = VdP – SdT, does not take into account any

variation in free energy due to concentration changes.

• We know Gʹ = Gʹ(T , P, n1 , n2 , ....)

• From the fundamentals of partial differentiation we have

⎛ ∂Gʹ ⎞ ⎛ ∂Gʹ ⎞ ⎛ ∂Gʹ ⎞ ⎛ ∂Gʹ ⎞

dGʹ = ⎜ ⎟ dT + ⎜ ⎟ dP + ⎜⎜ ⎟⎟ dn1 + ⎜⎜ ⎟⎟ dn2 + ......

⎝ ∂T ⎠ P ,ni ⎝ ∂P ⎠T ,ni ⎝ ∂n1 ⎠Texcept

, P , n2 ....

n1

⎝ ∂n2 ⎠T , P ,n1 ....

except n2

∂G '

= S'.dT + V' dP + ∑ dn i

∂n i T , P , n1 ....

except n i

⎜⎜ ⎟⎟

denoted by µ hence⎝ ∂ni ⎠except

P ,T , n1 .......

n i

Chemical Potential

⎛ ∂Gʹ ⎞

⎜⎜ ⎟⎟ = µi

⎝ ∂ni ⎠TExcept

, P , n1 .....

ni

µ is an intensive variable

This gives a new sets of fundamental equations for the open systems.

Physical Meaning of Chemical potential

• Consider the change in free energy (dG/) of a system produced by the

addition of dnA mole of component A at constant pressure and temperature.

The change in free energy of a system is given by dG ʹ = µ A dn A = G A dn A

is the partial molar free energy of component A in solution

⎛ ∂G ʹ ⎞

G A = ⎜⎜ ⎟⎟ = µ A for a large quantity of solution

⎝ ∂n A ⎠ P ,T , n B

⎛ ∂G ⎞

G A = ⎜⎜ ⎟⎟ = µ A for one mole of solution

⎝ ∂n A ⎠ P ,T , n B

• Chemical potential of either 1 g mol or 1 g atom of a substance dissolved in

a solution of definite concentration is the partial molar free energy. Thus

Maxwell s equations

⎛ ∂M ⎞ ⎛ ∂N ⎞

equation: dZ = M dX + N dY, ⎜⎜ ⎟⎟ = ⎜ ⎟

⎝ ∂y ⎠ X ⎝ ∂x ⎠ Y

⎛ ∂T ⎞ ⎛∂P⎞

⎜⎜ ⎟⎟ = − ⎜⎜ ⎟⎟

⎝ ∂ V ⎠S ⎝ ∂ S ⎠V

⎛∂T ⎞ ⎛∂V⎞

⎜⎜ ⎟⎟ = ⎜⎜ ⎟⎟

Maxwell s relations are used

⎝ ∂ P ⎠S ⎝ ∂ S ⎠ P

frequently in thermodynamics

⎛ ∂S ⎞ ⎛∂P⎞

⎜⎜ ⎟⎟ = ⎜⎜ ⎟⎟ for the calculation of changes in

⎝ ∂ V ⎠T ⎝ ∂ T ⎠ V

thermodynamic variables for

⎛ ∂S ⎞ ⎛∂V⎞

⎜⎜ ⎟⎟ = − ⎜⎜ ⎟⎟ different processes.

⎝ ∂ P ⎠T ⎝ ∂ T ⎠P

Thermodynamic Mnemonic Square

involving the different thermodynamic potentials Max Born

suggested a diagram known as Thermodynamic Mnemonic

Square. T

V A

• Four sides of the square are leveled

in alphabetical order starting from the

top and moving in clock-wise direction

with four thermodynamic potentials

U G

namely A, G, H, U.

S H P

• The other four primary functions namely V, T, P, S are placed at the four corners in such a way that

each thermodynamic potential is surrounded by the condition under which it acts

We can write the total differentials of each of

potentials with help of this diagram as follows:

– Differential of any potential is equal to the sum of the differentials of its

adjoining variables with their coefficients equal to diagonally opposite

variables.

– This coefficients are taken to be positive if arrow points away from the

variable and negative if it points towards the variable.

dG = - S dT + V dP

Maxwell s relations can also be read from the

diagram as follows:

– It is required to consider the corners only

– The square is rotated in anti clock-wise direction in such a way that the

function whose partial differential is to be arrived it appears on the top

left hand corner of the square.

– The partial derivative of this variable w.r. t variable on the bottom left

hand corner keeping the lower right hand corner variable as constant is

equal to the partial derivative of the top right hand corner variable w.r.t

bottom right hand corner variable with bottom left hand corner variable

as constant.

– Negative sign on the right hand side of the equation is put if the arrows

are placed unsymmetrically with respect to vertical axis drawn from

centre of the square on rotation.

⎛ ∂T ⎞ ⎛∂P⎞

⎜⎜ ⎟⎟ = − ⎜⎜ ⎟⎟

⎝ ∂ V ⎠S ⎝ ∂ S ⎠V

Standard state of free energy

atm pressure and at its stablest state at the

temperature under consideration.

calculated when the reactants and products are

present in their standard states is called the standard

free energy change.

value of free energy but change in free energy is

quite possible to measure.

• Therefore, there must be some reference point

with respect to which the actual values of

various substance can be calculated.

• The free energies of stable form of the elements

at 298 K and 1 atm pressure are arbitrarily

assigned as zero value.

• The free energy of formation of compound are

calculated on the basis of the above

assumption and the value is described as

standard free energy of formation.

• This quantity is generally reported at 298 K and for compound say MO, it

would be written as ΔG0298, MO.

• The Hess s law is applicable for calculation of free energy change as it is a

state property.

• The standard free energy of formation of compound and the standard free

energy of compound are same.

M + ½ O2 = MO 0

0

ΔG0298 = G0298,MO - G0298,M - ½ G0298, O2

ΔG0298,MO = G0298,MO

For the reaction

a A+ bB → cC + d D

the s tan dard free energy change ΔG 0 at 298 K is given by

= c G 0298, C + d G 0298, D − a G 0298, A − b G 0298, B

the s tan dard free energies of reac tan t and products must be known

Some thermodynamic

relationships

By definition G = H – TS = U + PV –TS

differentiating dG =dU + PdV + VdP – TdS – S.dT (1)

Assuming a reversible process involving work due only to

expansion at constant pressure

According to First Law: dU = dq – PdV and from Second

Law: dq = TdS

∴dU = TdS – PdV (2)

From (1) and (2) we get dG = (TdS – PdV) + PdV + VdP

– TdS

– SdT

or dG = VdP – SdT (3)

Some thermodynamic

relationships

⎛ δG ⎞

At constant pressure, dP = 0, so that ⎜ ⎟= - S

⎝ δT ⎠ P

and at constant temperature, dT = 0 and ∴dG = VdP

RT

from PV = RT for ideal gas, dG = dP

P

Integrating between the limits PA and PB at constant

Temperature PB

dP P B

ΔG = G B − G A = RT ∫ = RT ln (4)

PA

P PA

if GA is the free energy of the system in its initial state and GB

the free energy in its final state when the system undergoes a

change at constant pressure

Some thermodynamic relationships

d (G B -GA )= (SB - SA )dT

but ΔG = GB – GA and ΔS = SB – SA and so that d (ΔG) = -ΔS.dT

⎡ δΔG ⎤

⎢ δT ⎥ = −ΔS

⎣ ⎦P

on substitution

⎡ δ (ΔG )⎤

ΔG = ΔH − TΔS = ΔH + ⎢ ⎥

⎣ δT ⎦ P ,T

Calculation of ΔG0 at high temperature

temperature from the ΔH0 and ΔS0 values at 298 K

(available in the literature ) in this way

ΔG 0T = ΔH 0T − T ΔS0T

T T

⎡ 0 ⎤ ⎡ 0 ΔC P ⎤

or ΔG 0T = ⎢ΔH 298 + ∫298 ΔC P dT ⎥⎦ − T ⎢ΔS 298 + ∫ dT ⎥

⎣ ⎣ 298

T ⎦

It must be remembered that if any transformation

takes place between 298 and T K in reactants and

products must be introduced in the above equation.

the temperature of a closed system of fixed ⎛composition

δqrev ⎞ is increased

⎛ dH ⎞ c p dT

Third law of Thermodynamics

dS = ⎜ per

2 at constant pressure, the increase in the entropy ⎟ =

mole =

⎜of the⎟system,

⎝ T ⎠P ⎝ T ⎠P T

by

and thus, if the temperature of a closed system of fixed composition is inc

Enunciation of third law

T

cp

∫

2

∆S from

= S(TT, Pto) −T S(atT constant

21 , P ) = pressure,

2 1 dT the increase in the entropy per mole of the s

(6.12)

The change in entropy with constant pressure

T1 T and constant volume is given by following

Δ

equations

S , is given by

CP

of entropy is obtained as thedT

dS = area under a plot of c p /T versus T between T2

cp

T ∆Sa plot

and T 1 , or, equivalently, as the area under

T 2 and lnT 1 . Generally,

CV

and dS = S T , the

= S(T − S(T1,lnT

of2 ,cPp )versus P) =

dT molar entropy of the system at any tem-

between dT

T1 T ∫

T

is given by

This

Integration of thischange of entropy

leads to the followingis obtained as the area under a plot of c p /T versus T b

HEAT CAPACITY, ENTHALPY,

the limits T 2 andENTROPY 173

TT 1 , or, equivalently, as the area under a plot of c p versus lnT b

cp

S

the limits

T = S

lnT +

∫

0 2 and lnT (6.13) of the system at an

dT1 . Generally, S T , the molar entropy

T the system at 0 K. In turn, the Gibbs free energy

0 of

where S is the molar entropy

perature T , is given by

0

can be written as

where S0 is the molar entropy of the system at 0 K.

T

cp

∫

T T

cp

∆G =

∫

0

cP dT − T

∫

0 T

ST −=TSS00

dT +

0 T

dT

If the entropy at 0 K is known, the thermodynamics of the reac>on is completely known

pletely known. This was proposed by Le Chatelier in 1888:

Third law of Thermodynamics

if the value of S0 for a reac>on could be determined, ΔG would be known as a func>on of

temperature as well, and hence, the reac>on thermodynamics would be known.

• These equations also state that for calculation of absolute value of entropy of any

substance, these constants should be known.

• In order to evaluate the constant, Nernst analyzed the low temperature data on free

energy and enthalpy of chemical reactions.

• The analysis lead to the formulation of first, the Nernst heat theorem and later the

third law of thermodynamics.

Third law of Thermodynamics

Nernst heat theorem

• Nernst collected enthalpy of

formation of various reactions

by calorimetric method and

determined free energies as a

function of temperature by emf

method.

enthalpy when plotted against

temperature yielded curves as

shown.

Third law of Thermodynamics

It is seen from the figure that at low temperature that both

enthalpy and free energy of a reaction approaches each

other asymptotically with the asymptote

174 laying parallel to TO THE THERMODYNAMICS OF MATERIALS, SIXT

INTRODUCTION

temperature axis. This lead Nernst to arrive at the following

conclusions: ∂ (Δ G )

(i ) Lim =0

T →0 ∂T

DHa®b

∂ (Δ H )

(ii) Lim =0

T →0 ∂T

As

⎡ ∂ (Δ G )⎤ DH(T1) Slope = –DSa®b

⎢ ∂ T ⎥ = − ΔS

⎣ ⎦P DGa®b

T1 T®

Therefore, one can write Lim Δ S = 0 Ga = Gb

T →0

Third law of Thermodynamics

Statement of Nernst heat theorem

It states that both entropy change and temperature

coefficients of enthalpy and free energy changes for the

reaction tends to zero as temperature approaches 0 0K.

Entropy of a pure substance

A pure substance is a pure element or pure compound.

Consider the formation of compound AB from elements A

and B i.e

A(s) + B(s) = AB(s)

For which ΔS0 = S0AB - S0A - S0B

At absolute zero temperature ΔS0 = 0 it is possible provided

0 0 0

either i) SAB = (SA + SB )

Third law of Thermodynamics

• From a probability point of view, the first alternative is very unlikely as a general

feature. It may be true, by chance, in a few cases.

• Hence alternative (ii) is accepted as of general validity and it may be concluded that

entropies of pure solids at T = 0 are zero

• Therefore, the absolute value of entropy of a pure substance at any temperature can

be determined by taking T = 0, S = 0 as the lower limit.

Third law of Thermodynamics

All reactions involving substances in the condensed state ΔS is zero at absolute zero

equilibrium may be taken as zero at 0 0K

The entropy of any phase whose quantum states and atomic arrangement corresponds

to a unique lowest energy state at the absolute zero is zero

Third law of Thermodynamics

Experimental verification

of the third law

• Third law is not so obvious as first and second law; hence it is required to describe

some of the evidence by which it was established.

• The so called direct verification of the third law involves the application of the

second law, namely the principle that the entropy of the system is a function of state

and the net entropy change experienced by a system undergoing a cycle is therefore

zero.

Third law of Thermodynamics

• Let us consider the cycle shown T

in the figure.

II

• The starting point is a system

composed of reactants at the

absolute zero. 0K

• The first step of the cycle

I

consists in heating the reactants III

to temperature T.

• The reaction is allowed to

completion at T in the second

step. IV

• The products are cooled to 0

0 % reacted 100

absolute zero in the third step.

• The fourth step which imaginary,

the reverse reaction is allowed to

proceed

∆SII = −(∆SI + ∆SIII )

where:

Ttrans

c p(α )

• We have from the second law ∆SI =

∫

0 T

dT

∆SII = = H (β, Ttrans ) − H (α, Ttrans )

Or ΔSIV = - (ΔSI + ΔSII + ΔSIII ) Ttrans

0

c p (β )

• ∆S =

Since the entropy change in the first three steps measured

III

Ttrans ∫ dT

experimentally,

T

the

entropy change at absolute zero can be determined.

• Let us consider the following transformation reaction DSII

Ttrans

DSI DSIII

0K

DSIV

a b

HEAT CAPACITY, ENTHALPY, ENTROPY

∫0 T

177

∆H trans

∆SII =

= H (β, Ttrans ) − H (α, Ttrans )

Third law of Thermodynamics

6.6 EXPERIMENTAL VERIFICATION OF THE THIRD

Ttrans

0 LAW

c p (β )

∆SIII =

Ttrans T ∫

dT

The Third Law can be verified by considering the phase transition of one mole

• The Third Law can be veriﬁed by considering the phase transi>on of one mole of

of an element, such as

an element, such as DSII

α→β α →β Ttrans

where α and β are allotropes of the element. In Figure 6.11, T trans is the temperature,

• at Tatmospheric pressure, at which the α and β phases are in equilibrium with one

trans is the temperature, at atmospheric pressure,

another. For the cycle shown in Figure 6.11,

at which the α and β phases are in equilibrium

DSI DSIII

with one another. ∆SIV = ∆SI + ∆SII + ∆SIII

the Third Law to be obeyed, ∆ S IV = 0, which requires that

∆SIV = ∆SI + ∆SII + ∆SIII

∆SII = −(∆SI + ∆SIII )

0K

For the Third Law to be obeyed, ∆SIV = 0,

• where: DSIV

Ttrans

a b

c p(α )

∆SI =

∫ 0 T

dT

Figure 6.11 The cycle used for the experimental verification of the Th

∆H trans Thermodynamics.

∆SII = = H (β, Ttrans ) − H (α, Ttrans )

Ttrans

0

c p (β )

∆SIII =

∫ Ttrans T

dT

∫0 T

∆H trans

∆SII = = H (β, Ttrans ) − H (α, Ttrans )

Third law of Thermodynamics Ttrans

0

c p (β )

∆SIII =

∫ Ttrans T

dT

The cycle shown has been examined for the case of

sulfur, which has two allotropes:

DSII

a monoclinic form which is stable above 368.5 K Ttrans

an orthorhombic form which is stable below 368.5 K

The molar enthalpy of transforma>on is 400 J/mole at

the equilibrium transforma>on temperature of 368.5 K

DSI DSIII

the varia>ons, with temperature, of the heat capaci>es of both

allotropes have been measured experimentally at

temperatures below 368.5 K 0K

DSIV

a b

Figure 6.11 The cycle used for the experimental verification of the Th

Thermodynamics.

∫ 0 T

∆H trans

is called the experimental entropy change , and – (∆ S I + ∆ S III ) is ∆ SII = the = H (β, Ttrans ) − H (α, Ttrans )

Third law of Thermodynamics called

aw entropy change . If the Third Law is valid, ∆ S II = – (∆ S I + ∆ S III ).

Ttrans

0

c p (β )

cycle shown in Figure 6.11 has been examined for the case of sulfur,

allotropes:

∆SIIIwhich

a monoclinic form which is stable above 368.5 K and an ortho-

=

∫

Ttrans T

dT

Since monoclinic sulfur can be super-cooled with rela>ve ease, the varia>ons, with temperature,

c form of the heat capaci>es of both allotropes have been measured experimentally at temperatures

which is stable below 368.5 K, with a molar enthalpy of transforma-

400 J/mole at the equilibrium transformation temperature of 368.5 K. Since DSII

below 368.5 K

inic sulfur can be supercooled with relative ease, the variations,Ttrans

with temper-

f the heat capacities of both allotropes have been measured experimentally at

atures below 368.5 K. The measured heat capacities give

The measured heat capaci>es give

368.5

c p( rhombic )

∆SI =

0 ∫ T

dT = 36.86 J/K DSI DSIII

∆H trans 400

∆SII = = = 1.09 J/K

Ttrans 368.5

0K

DSIV

0

c p( monoclinic )

∆SIII

∫

368.5 T

dT = −37.8 J/K

a b

Figure 6.11 The cycle used for the experimental verification of the Th

Thermodynamics.

( ∆SI + ∆SIII ) = − ( 36.86 − 37.8 ) = 0.94 J/K

s is the value of the Third Law entropy change. The value of was shown to be 1.09 J/K

The value of the experimental entropy change ∆S the experimen-

II

opy change ∆SII was shown to be 1.09 J/K. Since the difference between the

Third law of Thermodynamics

Consequences of the third law

Third law leads to following important consequences

1. CP, CV and α will be zero at absolute zero.

G=H−TS

⎛∂G ⎞ ⎛∂H⎞ ⎛ ∂S ⎞

⎜⎜ ⎟⎟ = ⎜⎜ ⎟⎟ − T ⎜⎜ ⎟⎟ − S

⎝ ∂ T ⎠P ⎝ ∂ T ⎠P ⎝ ∂ T ⎠P

⎛∂G ⎞ ⎛∂H⎞

As we know ⎜⎜ ⎟⎟ = − S and ⎜⎜ ⎟⎟ = C P

⎝ ∂ T ⎠P ⎝ ∂ T ⎠P

⎛ ∂S ⎞

we can write C P = T ⎜⎜ ⎟⎟

⎝ ∂ T ⎠P

⎛ ∂S ⎞ Prove that CV is zero

as ⎜⎜ ⎟⎟ is finite , at T = 0 ⇒ C P = 0

⎝ ∂ T ⎠P at absolute zero

Third law of Thermodynamics

1 ⎛ ∂V⎞

α = ⎜⎜ ⎟⎟

V ⎝ ∂ T ⎠P

according to max well' s equation

⎛ ∂V⎞ ⎛ ∂S ⎞

⎜⎜ ⎟⎟ = − ⎜⎜ ⎟⎟

⎝ ∂ T ⎠P ⎝ ∂ P ⎠T

⎛ ∂S ⎞

as T → 0 , S → 0 so ⎜⎜ ⎟⎟ =0

⎝ ∂ P ⎠ T →0

⎛ ∂V⎞

⇒ ⎜⎜ ⎟⎟ = 0 ⇒ α = 0

⎝ ∂ T ⎠P

Third law of Thermodynamics

2. Unattainability of absolute zero temperature

let us consider a carnot cycle in which heat is absorbed at temperature T (T > 00K)

delivered to cold reservoir maintained at 00K. Entropy change during such a cycle will

be equal to zero i. e.

ΔSI + ΔSIII = 0

where ΔSI is the entropy change during isothermal expansion and ΔSIII is the entropy

change during isothermal compression.

Third law of Thermodynamics

According to third law the entropy change during isothermal

volume change (ΔSIII ) at 00K is zero. Hence ΔSI will be zero.

But this not true as both heat exchange and temperature for

this is finite non-zero and positive.

the working substance descend to the absolute zero.

be attained.

Third law of Thermodynamics

3. Calculation of entropy and free energy from calorimetric data.

Entropy of a substance at constant volume is given by

T

SV = ∫ C V d ln T + S0,V

0

T

therefore, SV = ∫ C V d ln T

0

From the knowledge of heat capacity which can be

determined by calorimetric techniques, one can

calculate the absolute value of entropy of a component

at any temperature T.

Third law of Thermodynamics

Third law also helps in the calculation of free energy during the

chemical reaction from the calorimetric data obtained in the

form of enthalpy of a reaction as a function of temperature. We

know ΔG = ΔH – T ΔS

T T

ΔCP

ΔS = ∫ d T and ΔH = ΔH 0 + ∫ ΔCP d T

0

T 0

T T

Or ΔC P

ΔG = ΔH 0 + ∫ ΔC P d T − T ∫ dT

0 0

T

All the quantities present in the above expression can be

determined by calorimetric techniques. Thus, one can calculate

the change in free energy of any reaction at desired temperature

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