fntroduction

To

Melallurgical Thermodynamics

R. H. Tupkary Ex Prof. & Head Dept. of Met. Egg.

V. Regional College of Engineering NAGPUR.

Itr

Pupir.sners ir-agpur t+o ozz

Published by Mrs. Mbha B. Saoji

SUMATI,41, Atre Lay-out, Nagpur - 4AO22

(Ph:pp. -0712-234f,73)

Legal Warning
This book as a whole or part thereof can not be reproduced in any forrn whatso e\,er, or translated, except for review or criticism in scientific literature, without the written permisssion of the author and the publisher

FIRST EDITION - 1995

erice

f $.15q/9

Printed at - Surya Offset ' Ranrdaspeth, 28 farm land Nagpur - 440 010

DEDICATED TO
All those scientists and technologists who are striving hard to raise the energy efficiencies of various
englneering and technological processes in lndia to bring these up to the best standard in the world.

Preface
Thermodynamics istaught at under graduate level in the degree course

of metallurgical engineering all over lndia and yet no appropriate book

is

available for the beginners to understand this most abstract and conceptual subject. The available books are rather too elaborate and orer exhaustive and an average student finds it difficult to separate out the required material for his purpose. The non-availability of an appropriate book becomes an handicap in understanding this abstract subject. lt may be one of the reasons why this subject is dreaded mosi by the students and the net result is that the subject,

which ought to be understood properly for understanding other subjects at higher lewls in metallurgical cunicula, is appreciated by the students only mechanically for the purpose of solving numericals alone.
Having taught the subject at the beginners level for over a decade these

difiiculties of students became more and more apparent. The desire to write an

introductory text book on thermodynamics for metallurgical engineering students became intense but availability of leisurely time was rather remote. This became available only while canvalescing after an accident in which both tibia
and fibula were fractured.
I hope the students will like this new addition afterthe earliertwo - steel

making and iron making - equally well. Even if the students do not find if so useful as the earlier two books, the pleasure of preparing the manuscript of the book on thermodynamics always made me forget the pains of a fractured leg
during the period of convalqscence. And now when the book is being published,

the unpleasant memories of the accident

been wiped out.

if not

fully, at least pontially have

I take this as if desired providentially.

Nagpur Makar Sankranti

1

P..

H. Tbpkary

995

Contents

l. 2. 3. 4 5. 6. 7. 8. 9.

lrtuoduction

' -

Scope, Concepb and terrre,

Ffustlawof Tbemod5mamics

15

hrbrtr.al Energr, E*raby ard theirdelvatives

Secondlewof ThemodSnramics Enhropy ard ib Derivatives

38
53 70 76 83

Thermod5nramic Fotentiatrs F\ee Ene1ry ard F,quilibrium Crfufu

ThndlawofTbermodJmamics'
Estimatbnof Enbopy

ZerothlawofTbermodynamics
Phase Sbbility

ChmicalEquilibdaFauilibrium Constant Phase Equilftria in Single C.,qmponent System Clausius - Clapeyron F4uation

9l
100
116

Sohrtion IGibbs -Drhem Equatio n anil Activily Laws

MDdng and
E><c e s

10. sohrtiontrs F\rrrc

tio

ns and,Re guhr

So

lutb n

11. Sohrtionltr
Applicatbns of Gihbs - Duhem F.quation

125

12. 13. 14. 15.

EquililsriainPhase
Emf I\lbasuremenb

nnagrams Hecfuocbemicalhocesses Ftee

-133

lM '
151

hergy-

Tbmperature Relationships

Eilingham Diagrams

IGnetics of Reactiore'
Process rates

180

Bbbg:aphy
Symtiob dnd Abbreviatio ns

n
Ily

[*lex

Acknowledgement
The author is indeed indebted to many in the preparation and publication ol this book in a very short span of time. I am grateful to all my earlier colleagues and staff members of the Department of Metallurgical Engineering, VRCE, for their constant encouragement in writting this book. Special thanks are due to Shri. A. P. Patil, lecturer, for his untiring efforts in making me conversant with computer-composing of the initial manuscript of the book.

I have no words to express my gratitude to Shri. Sandeep Gadge for his uncomplaining help in the preparation of the final manuscript on D.T.P. of the Shri. Narkesary Prakashan Ltd,, Nagpur. I am equally thankfulto Shri. Ajay Dhakras of M/s. Surya Offset in getting this book printed in almost record time. I have deep sense of appreciation of my wife Mrs. Madhuri and chlldren, Vidyesh and Shailesh, without whose suggestions and constructive eritiiism this book would not harle been in the present elegant forrn.
The scientific tradition as exemplified by the folloWing quartet
r rE[$lfli[E[rE[ zfftlq[: cfulffi:

ggffigT
I

T{dr qRE rrqrfr +treFilFt:

cim'Sir -Rerq sn+r$

g*: {dE: .

rHr

*'+-6{rqAq

F*

qqrgwrqq'

I ir

always inspires me to contribute my liftle might in regaining that scientific glory of our

nation. May this piece of scientific work be my humble offering at the alter of our
beloved motherland. R. Fl. Tupkary

CHAPTER

lntroduction
scope, coneePts and terms

1.1 l-llsroRlcAL 1.1.1 Energy in Historical Perspective

available i'e' The stone-age man sustained himself by eating whaterrerwas naturally He must have green fruits, roots, dead animals, etc" and perhaps resided in natural caves' energy thermal the to due felt the warmth of the bright sun withottt knowing that it was same associated with the sun rays. He must have accidentallydiscoveredfireandfeltthe gradually understood warnrth that he experienced in sun-rays. With the passage of time he leaves and chips dried the need of cooking his food, aibeit crudely, may be on fire lit by burning crude implements made out of branches of trees or pieces of stones
of

to build crude habitat made might have been developed by him and similarly he appreciated out of similar naturatly occurring materials like bushes and trees' some labour for sustaining He was moving around in search of food thereby doing some work' The human energy himself out of natural instinct. ln modern terms he was doing illustrated here by was being used to do work. This is true of all beings of animate world,

trees. slowly some

being is the energy that is the example of hurnan being. The food consumed by human work' A dead man does not converted through biological and physiological processes into days the food consumed by do such work because he does not consune food. ln modern food he consumes' A robust a human being is assessed in terms of calories equivalent of

manconsumesmorefoodancJ,atleast,iscapableofdoingmorework' man As the human civilization prcgressed from stone-age into the bronze-age their of copper and tin from appreciated and developed the art and science of extraction useful implements for minerals, therby producing alloy bronze and its conversion into been used in this extraction sustaining his civilization. The chemical energy of coal must have

This is really the beginning of use operation without understanding it as is understood today. and tin minerals, into useful of energy for chanEing the existing materialforrns, i.e. copper implements for better human life. use in the development The same is the story for all materials that slowly came into to of hunran civilization since the stone- age. The bronze-age progressed into iron-age

use of mankind' This produce a much wider range and better quality materials for the its rnodem form into further uttimately brought in the industrial rewlution and progressed

through the enormous engineering and technological activities. Alltbe modern manufacturing activities are nothing but changes brought about in the existing chemical, physical and mechanicalforms into new forms. For example, iron ore is
reduced by carbon to produce iron and then converted into steel. Steel is processed to produce varieties of forms and shapes. A tree is finally conrerted into a chair or a table. A bamboo is converted into a paper which is then made into a notebook. All these are changes deliberately broughtt into the existing material forns for the benefit of mankind. Without these manufacturing activities the present day human civilization just could not exist.
ln fact the history of human civilization is nothing but progressive increase in anpunt, quality and cornplexity of materialsmadeavailablefortheuse of mankind. This was all possible because industrial revolution could obtain energy on an increasingly larger scale, hitherto unknown, for the benefit of rnankind. No wonder the quality of human civilization is assessed in terms of per capita' consumption of various materials, in particular the basic materials like steel, aluminium, copper, etc. or per capita consumption of energy like

electrical energy. Energy was available to the stone-age man as is available at least in the naturally occurring forms. He however could not use it because he could not harness it as is possible today. lndustrial revolution is a 'revolution' in terms of h4rnessing the available energy. The steam engine is the device that was invented first to convert essentially the chemical energy of coal, by first converting it into thermal energy, and then into mechanical energy and thereby started off the industrial revolution. Consequently the railway train, textile mills, tool manufacture and so on got off on hitherto unknown larger scale.

Soon chemical energy could be converted into electrical energy in thermal power plants and manufacturing activities carried out on increasingly larger scale using electrical power. Electrical energy could be generated by constructing dam, on rirrcrs. The potential energy of water , so stored, was subsequently converted into electrical energy through hydel generators. Similarly chemical and electrical energy was interconverted as per need, through electrochemical cells to produce one from the other. This finally culminated into the development of almost infinte source of energy through conversion of mass into energy through nuclear reators, which is nothing but a miniature form of celestial star, a perenial
souce of energy on earth.

lf one looks at the history of human civilization from the point of vieur of energy r.rtilization, few facts come out quite vividly. 1. The human energy is limited and hence the work that can be carried out manually is limited. lt is estimated that a, human being can offer energy equivalent of about

2. 3. 4. 5.

horsepower. Externalenergy is required to obtain new rnaterials and in their new forms. Energy is required to produce materials in their proportion, quality, complexity, etc.

1lB

Use of more and better materials is rasponsible for the developmwnt of hunran
civilization starting from the stone-age upto the modern super industrial civilization. lndustrial revolution is nothing but the development of means of harnessing energy for the benefit of mankind.

ln energy terms therefore, the history of

development

of means of

human civilization is nothing but harnessing energy in ever increasing proportion, from and.in its

varied fornrs, for the benefrt of mankind. The present day civilization sustains itself on its tremendous capacity to bring about changes in existing material forrns. A change may occur as a natural one, for example, brought burning of coal, accompanied by evolution of energy. However most changes are to be about by supply of energy from outside. These are unnatural changes typically illustrated by the example of extraction of metals from its rninerals. The necess'rty to evaluate the energy requirements for such changes and the progressiw decrease in the landmark dev'dopment in human civilization' 1.1.2 Thermodynamics in Historical Perspective The establishrnent of industrial revnlution on a firm footing by the eighteenth century, as was the resutt of human ingenuity, was also the eause for further development

actual energy consumption by way of the improrements in such activities has been one of the

human ingenuity, quite naturally, compelled these 'revolutionaries' - the men of science, to understand the scientific principles underlying the means adopted for harThe early nessing th6 therrnal energy readily available from burning of chemicalfuels'

of

energy approach was essentially related to the steam engine- a device that converted therrnal of thermal into mechanical energy. This eventually crystalised intothe study of this dynamism quite sometimes energy into what is now known as the 'science of thermodynamics'. For the only energy was energy even after the cornrnencement of industrial revrlution thermal of form available to be harnessed for useful industrial activities.This is the origin of science thermodynamics.

of With the progress of industrial revolution on the one hand and development of forms other science as a whole on the other, led the scientists to discover ser,eral of energies like electrical, electrochernical, magnetic, nuclear and so on' The harnessing these of of interconversion these energy forms inrolved the development of means energies. The science of thermodynamiqs had to deal with each one of these interconenergies, as it appeared on the scientific horizon. The traditional name howerer

version of ai times did not at continued to be used for all such studies although the interconversion all involve thermal energy as such. Strictly speaking therefore the science of interconversion cover allforrns of energies need to be named anew as something like 'energodynamics'to to be referred to the of energies, but the same traditional name thermodynamics continues study of interconversion of energies. years but The science of thermodynamics really developed over the lastfew hendred

1906 more so in the last century, The formulation of Nerns't Heat Theorem in completed the formulation of 'elassical thermodynamics' i.e' the laws of thermodydesire namics and related mathematical deductions. lt should be remembered that the and the necessity to assess theefficiencyofsteamengines,theninuseforquitesonretime' Hence more than anything else, led to the derrelopnrent of classicalthermodynamics'

engine or the related mathernatical deductions are often illustrated with reference to a steam

in its

idealised form as an idealgas engine'

1.1.3 Scope of Metallurgical Therrnodynarnics

The science of thernnodynamics here 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 with
separately because in that case all matter would have to be considered as forms of energy as per the famous Einstein equation E = mC2 . The nuclear thermodynarnics is altogather different branch and in order to distinguish the general thermodynamics the terms chemical or metallurgical or mechanical thermodynamics have been introduced lately. Here the subject matter of discussion is chemical and/or metallurgical thermodynamics alone. The systems under discussion will be one of finite dimensions consisting of a large number of particles, i.e. macro systems.

.I"2 THERMODYNAMICS AND RATE OF CHANGE

The knowledge of thermodynamic science may indicate the possibility of the change but it does not indicate in any way the time required to bring about the change i.e. the rate of the change is not predictable by thermodynamics. The rates of changes are studied under a separate brach of science known as science of 'kineties' which helps to assess the time required f6r a certain change to occur vis-a-vis the physical configuration of the system' This can best be illustrated with the help of the following example :

The loss in potential energy or more appropriately the exehange of energy as the water flows under gravity is the same irrespective of whether the outlet is say 10 mrn dia,

25mmdia orintheextremeacapillary.Butthetimerequired for a ceftainamountofwater to flow down varies considerably in these cases. lri other words the rate of exchange of energy is different in these three cases' More appropriately the rate of thermodynamic change is different in these three cases and it depends on the physical nature of the system. 1.3 EI\IERGY is the abilityto do work, useful or otherwise. This is too mechanical an answer. lfsulphuricacidandwater are mixed, even gently without much mechanicalwork, heat is produced. Where was this thermal energy residing earlier? in the
What is afterallenergy? lt acid or in the water? Similarly if silicon is dissolved in iron huge amount of heat is produced. Where was it earlier that it is evolved on dissolution? Having once established through the famous Einstein Equation E = mC2 that even mass is a condensed form of energy, the whole universe is nothing but energy in its various forms, like mass, thermal, kinetic, chemical, rnagnetic, etc. On terestrial level also it is true to the extent lhat everything is in terrns of energy. Quite obviously the energy associated with di{ferent material forms is different and therefore when one form changes to another the energy eitlrer gets liberated or is absorbed in one or the other forms of energy.

As a corrollary energy may be used to bring about changes in material forms, Natural changes in material forms are accompanied by evoltttion of energy, e'9. burning of coal, whereas unnatural changes have to be brought-in by investing energy. Natural changes are nol many. Even many such have a history such that earlier it had been

unnaturally brought into the forrn, like water stored in overhead tank, that now it flcnars down as natural change. Unnatural changes in material systems are necessary to produce so many materials for sustaining human civllization. Therefore nothing will change unnaturally from as-is-where unless some energy is invested to bring about that change' Energy is therefore capaclty to bring about ehanges in the existing nnaterial forms as per requirements. This definition is much broader than the mere ability to do

mechanical work. Some material forms possess so rnuch energy that given a chance they will undergo changes on their ourn, liberate excess energy and take a more stable, lo+v energy level, material forrn in consequence. Understandably such material forms are unstable because of higher energy associated with them. Ely and large naturally occurring materialforrns are not at high eneregy level and are processed on industrial level to produce a variety of material forms required for human civilization. These manurfacturing activities therefore require energy' The industrial manufacturing activities are such that more than the theoretical energy is always required to carry out these industrial activities. This gires the energy efficiency of the manufacturing operation. This energy efficiency is one of the most irnportant parameter that affects manqfacturing economy and is under constant survillence for improvement. The thermodynamic study is relevrant from this point of view' 1.3.1 Energy ProPerties The reader upto this stage is familiar

with

mass, pressure, temperature and volume

as these are far less abstract icjeas. One can feel or almost 'see' these p;'operties. Although energy exchanges during heating or cooling or phase changes can be assessed in terms of these simple properties, these properties by themselves are not adequate enough to assess energy exchanges during most of the changes. One of the simple reason for such an inadequacy is that these properties are not by thernselves energy paranreters as such. There must be sorne energy parameters or properties of maierials such that during any change, and change they will, so that the energy exchanges would be assessible direcily in terms of such energy pararneters. The thermodynamic science has evolved several such properties of materials which are energy parameters and by mere algebric summation of their values before and after the change can rer,eal the possible energy exchanges in the changes. The following
examples can be cited as illustratlons. A system takes some heat and in return does some work. Where is the balance energy 1. ? The theimodynamic science calculates this in terrns of changs in 'internal energy'

which

2.

energy Parameter. A liquid is converted into vapour at the boiling point without changing the pressure and the temperaturel The latent heat is provided foi'the change. The question is where and in what form the energy of vaporisation exists after vaporisation. The tliernlodynamic science evaluates this in terms of a property called - 'entropy'of a system and which is a energy parameter' A metaland oxygen combines to form the oxide. ln what form the energy is lost from the materials ? The thermodynamic science assesses it in terms o{ either 'enthalpy

is a

3.

4.

or free energy' which are yet another energy parameters. When electrolysis of a solution or an electrochemical reaction takes place it is thermodynamic science that can assess the energy exchange in terrrs of enthaly and free energy parameters of the chemical reaction taking place.

1.3.2 Thermodynamic Laws

The observations on changes taking place in this universe have led to evolve sorne definite facts which were formulated in due course of time into specific statements knownas theThreeLawsofThermodynamics.TheZeroth Law carne uplater. Although there is no direct proof to prove the validity of these thermodynamic laws but their applications to various changes taking place in this universe do yield correct results. These latrvs are applicable to finite changes in materials of finite dimensions consisting of large number of particles. These laws can not be applied to changes in materials of infinite dimensions such as on an universal scale or equally to micro-systems of just few atoms
or molecules.

1.3.3 Fornns of Energies

Since the thermodynamics deals with energies in all its forms it would be worth-while

to know the possible forms

of energies in material aggregatas.

The concept of energy is foremost in modern science and it is the basic consideration in manufacturing processes from the point of view of process economy. Yet the concept of energy is not obvious. The concept of kinetic energy became apparent first, potential energy inalienably follored. ln 1851 Lord Kelvin defined energy as, "The eilergy of a material

system ls the sum expressed in mechanical units of work, of all the effects which
are produced outside the system when the system is made to pass in any manner from the state ln which it happens to be to a certain arbitrarily fixed initial, i.e 'standard state'.". lt became obvious that there is nothing like absolute energy but only relative energy and that only energy changes can be measured. From the point of view of chemlcal and metallurgical engineers kinetic energy is seldom of interest. The total energy devoid of kinetic energy is called 'internal eneregy'.

Energy has also been defined as capacity to do work. Work is considered to be done if a body moves under the influence of force applied on it. Therefore

w=fxd
where f is force in dynes and d is the distance of movement. Work is measured in terns of erg in C.G.S. and Joule in S.l. units.

Joule =

107 ergs

ln otherwords what is capable of doing work must possess energy. Energy manifests itself in variety of forms like thermal (heat), mechanical (in tern-rs of movements), electrical (in terms of flow of electrons), chemical (in terms of bonds), nuclear (in terms of mass) and

so on. Except the nuclear all other forms of energies and their interconversion conversion to work specifically shall be deait with in the text to follorro. Mechanical; i) kinetic energy = 112 x m15S x velocity

and

ii) potential

energy

iii) congifurational

= =

lrllss

height

acceleration component

integralforce

distance over energy certain limits

Thermal :Heat exchanged

= = =

rrass
cuffftt

specific heat

temperature difference

Electrical :Electricalenergy

x time x

potentialdifference'

Chemical:Chemical energy nurnber of chemical

bonds

bond strength

't.3.4 Sources of EnergY

Although theoretically errcrything in this universe is energy, practically the resources of energy are limited. The naturally occurring materials which on mere initiation undergo changes into materialforms, and thereby liberate energy during the natural change, are one of the chief sources of energy on the earth. The coals in all their forns, mineral oils ancj natural gas on burning give thermal energy which is either used directly or converted into electrical or mechanical energy. This is the chief source of energy and these materlals are classed as chemical fuels. Fr.lel is considered to be synonymous for source of energy' Water stored, naturaly or artificially by dams at high levels has potential energy which can be convefied into electrical energy by hydel generation and hence is a source of energy. These are conrrentional sources of energy. With the rise of modern civilization into a enorrnous manufacturing activity the energy requirement is ever increasing. The natural sourcs of energy are limited and hence attention is focussed onto alternate sourees of

energy. ln this category cornas utilization of heat energy of sun-rays or kinetic energy of winds and tides, by converting them into suitable energy forms preferably electrical, mechanicalorthermal. The bio-gas generation by disintegration of vegetables and bio-mass also comes in this category. The nuclear energy available from fissionable materials like uranium was considered to be a very good potential source of energy on earth but the hazards associated with its waste disposaland the necassity of high safety standards has posed great hurdles in its full development as a source of energy. The initialeuphoria in this field in the fiftees has

now dampenedconsiderablY
The advantages of chemical fuels as a source of energy is that it can be stored and carried conwniently and useid as and when required . On the contrary electrical energy can be conveyed over hundreds of kilorneters within no time but can not be stored readily. lt must be used when available. Energy can be stored through chemical cells but the investment required

is rather too large.

It would be worth while to define certain tern'rs before understanding

1.4

TI-IERMODYNAMIC SYSTEM

the thermody-

namic laws. Since

the laws

of thermodynamics

are applicable to matedd aggre-

gates offinitedimension,awell defined finiteaggregate of materials has tobe visualised or in reality - constructed for the application of these laws and their derivatives for precise deductions. Such an aggregate of the material or a portion of this infinite universe, with real or imaginary dimensions, is referred to as a 'thermodynamic systefii', quite often for the sake of brevi$ only a 'system' . ln a dynamic bulk a portion of it can be imagined with finite imaginary boundaries as a system. The space or materials around this therrnodynarnic system under consideration ls generally referred to as '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
with the surroundings or on its in Fig.1.1.
orrun

material distribution or on its

o\,vn composition as shown

THEROMODYNAMIC SYSTEMS
IN TERMS OF ITS

INTERACT]ONS THE SURROUNDINGS

BASED ON MATERIAL DISTRIBUTION

COMPOSITION

ISOLATEDgCHANG.
ES NEITHER

OPEN BOTH
MATTER AND
ENERGY EXCI.IANGE OCCURS

CLOSED CAN

SINGLE

MULTI-COMPONENT

E(CHA.
NGE

MATTER
NOR

Ei fi O

Q,A Xu

f,ur

EN E RGY

ENERGY
WITH
INGS

BUT NOT
MATTEB

THE

fr$
:E>

H@

de

83 z= uJo9q
Xe
=a

r--l
@

COMPONENT

3 2
=

Eq

@o ri o l) tr)o

a :)

SURROUND

U.r /F o o

32iH ^ft; != qlH6 U^ *u) oX(E 5xg irJv aoi! J!I

==

Fig. 1.1 - Classification of tkermodynamic systems. Atherrnodynamicsystemmust, of necessity, be stablewithrespecttoitschemistry during its study. lf inherently the system is undergoing continuously some chemicalchange it can not be considered as a thermodynamic system. For example a live animate body like tree or a human being are not systems because they are continuosly unclergoing some changes - the life sustaining processes. Similarf a closed circuit Daniel cellcan not be a system because the anode and the cathode chambers are continuously undergoing chemical changes. On the other hand almost all of the inanimate aggregates of well defined bounddries can be called thermodynamic systerns as their chemistry is fixed (systens in which extremely slcryrr chemical processes are going on are exceptional). There can be sorne peculiar unstable chemicals which may not fall under the category of systems but these are exceptions. ln short there must be complete-internal- chenoical-stabilty for anything to be called as a thermodynamic system.

1.4.1

State of System

The system has to be described by some experirnentally determinable paranreters so that it can lead to its complete description and is understood by one and all as that particularsystem. For exampleforasinglecomponent homogeneous systerntherefore only two variables are to be fixed out of the three viz. pressure, rolurne and temperature for its complete description. Such variables are known as 'state 'variables. The minimum number of variables required to describe the state of the systenn are called 'independent' state variables. lt is also referred to as 'state properties'. The state of the system can also be described in terrns of energies associated with it' The algebraic surnmation of the energy parameters of the systern in two different states gives the energy exchanged during the change of the system from the initialto the final
state.

T.5 EXTENSIVE

AND INTENSIVE PROPERTIES

lf a state variable, whether dependent or independent, is a function of the mass of the system it is known as 'extensive'state property e.g. volume, energy properties, etc. lt only means that these properties get added up in proportion to thelr mass or the size of the system and are expressed per unit rnass like per gram mole. lf hower,er the function is independent of the rnass or size of the system it is called 'intensive' state property like density, temperature, pressure, conductivity, etc. These are not additive properties. For example when one gram of a substance at T degrees absolute is added to say a ton of similar material at the same temperature the resultant temperature is still T degrees only. Product of an intensive and an extensir,re properties is also an extensi\,e state variable whereas the rario of two extensive properties yiels an intensire propefi. The values of extensive properties, expressed per unit quantity of the system or substance, become intensive variables like specific volume, specific heat, partial properties, etc.

1.6

EQUATION OF STATE

The state of ihe system can be described in the equation involving some state variables.

form

of some mathematical

This analytical {orm as applicable to the system under consideration is known as 'equation of state'. For exarnple the pressure, volume, temperature and mass of an ideal gas are interrelated by an expression as

PV = nRT

(1.1)

where n is the nurnber of moles and R is the universal gas constant. This is the equation of state of ideal gas. Therefore if any two variables are fixed the third is automatically fixed for a giwn mass of ideal gas. The abow relationship is an exprassion which correlates the pressure, ternperature and volume of an ideal gas. ln fact this is found to be true in case of solids as well as liquids though the exact form of this relationship may not be known. The same can be described in a generalised functionalform as
F

(P,VT)

(1.21

It only means that there exists a function for every substance in any form which correlates pressure, volume and temperature. lt is not even remotely implied that it must be known. lt

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 state that particular system. These are useful relationships to calculate the required properties' knowing sone others. 1.7 THEREMODYNAMIC PROCESS
constraints, in terms of variables. such a change

ryray

or

it

nray not be known.

A material

system may undergo

a'thermodynamic process'' physical one of breaking lf a ten meter long rod is cut into two pieces the change is merely a it into two pieces. But if in the process of breaking, the energy required to break the rod is a thernnodynamic taken into consideration then the process of breaking is considered to be simple chemical a it is its oxide, to form process. similarly if iron combines with oxygen then this process process but if the energy exchanged in this process is taken into account process takes place of oxidation is a thermodynamic process' The way the thernndynamic processes ,process of thermodynamic path'. There are different types is known as its
in the state of the system is known as

a change, under externally or internally irnposed their state variables, from the existing one to sorne different

named accordingly and are depending upon the conditions imposed on the system and are shown in Fig. 1.2.

lsoBARlc

Fis.12 tr E f |o rt lt

g G o
o g
(,

tion of pressure vs. volurrte in vqriSc he

matic

re Pre s e nta

ous

tkermodYnamic Proc-

.ss'es

like

isabaric,

o.

kolhermal, isochoric, adiabatic and polytroPic-

VOLIJME
delsothermal - ln which temperature remains constant and is mathematically jacket with a thermal scribed as dT = 0. lt is imagined that the system is in contact maintained at the required temperature' imagined that lsobaric - ln which pressure does not change and hence dP=o' lt is
10

the procass is carried out in open atmosphere or in a vessel where the pressure is maintained constant.

lsochoric - ln which volume does not change and hence dV

process is carried

out in a vesel of known volunre. Adiabatic - ln which no exchange of heat occurs with thesurroundings and hence dq = 0 and is described as PV as constant. It is assumed that the process is insulated from the surroundings perfectly. The F or
V may change as per the given equgtion.

= 0. lt neans that the

Polytropic - Those processes which obey equation P\d is constant whereXis any positive number between one and y but not equal to either of them. ln this all variables can change but since any two can determine the third therefore, only two vary and the popular form of this equatlon therefore takes the form involving P and V only,

1.8

PATH ^AND STATE FUNCT1ONS

It is easier to visualise that the change in pressure, volurne dr temperature during a thermodynamic process is entirely related to the original state of the system and the final state to which it has changed to. lt does not depend on which way or by what process path the change has actualiy occurred. For example if a gas is expanded from say a urlume of 10 meter cube to 15 meter cube by an adibatic or isothermal chahge, the change in volume is obtained by algebraic summation of the two end states and it is 5 meter cube in this case. The same is true of temperature and pressure. The property whose change depends on only the initial and the finalstates of the system and not on the path adopted tobringaboutthe change,iscalleda'statefunetion'. Mathematicallythereforeiftheproperty is a state function then in a cyclic process, when the system undergoes a change but returns back to its original state, the net change in the state property or function is zero, lf r is the state function then

fdr =

(1.3)

and if say 1 is not a state function then f dy need not necessarily be equalto zero, where g indicate the integral over the entire cyclic chanEe. As against this there are properties such that the change in them in a process depends on the path followed for this change. It is interesting to note that energy is compounded of two terms nanely, heat and work effects
produced outside the system, neither of which are uniquely related to the state of the system.

Let us consider a gas being compressed or expanded from state A to state B as shown in Fig. 1.3. lt can be changed from state Ato state B i.e, from configuration Pr Vr to Pz Vz by any of the courses 1;2, or 3. The work done in such a case shall be the area under the relevrant curve from Ato B, and it shall be integral PV. ln course 'l the process is carried out isothermally. ln course 2 it is first by cooling follcnrued by heating-and in course 3 it is first by heating followed by cooling. The work done in all these cases is different though the initial and final states are exactly the same, because of different paths follovrred in these cases. Therefore the work done by making the system change from state A to B is not a function of states A and B but it definitely depends upon the path

adopted

for the

change, $imilarly

the ability to absorb or desorb heat i.e.

11

heat

in
c
lrt
rtt

Fig. 1.3 - Schematic P-V dingrant

showing the expawion and contrac-

lg1
aa

o,
02

lion of a gus between stateA depicted by Pt Vt and stcte B depicted by p2

Vz.

V1

-'+ *Vb'"frfr?E"

v2

exchanged

in the process depends on the path followed. Hence work done w or heat
but path functions. state functions is also obMous from the above example

exchanged q are not state functions

The usefulness of

because mere algebric summation of the values of the state functions gives the change in the state but in this instant case of assessing the work and heat exchange effects such a summation does not lead to the required value as these are not state functions. Whether

any function is

a state function or not can be mathematically assessed as follcnrus. For an ideal gas T = PV/R wherein P and V are taken as independent variables and T as

dependent variable. The above can be expressed in its total differential form as

dr =

(#)

dv

(#) .'
x
Ndy

(1 4) and y and any third function (1.5)

generalised form if a system has two independent variables say z can be expressed in its total differential form as ;

dz = Mdx+
only if

where M and N may be functions of x and y hence function AN

AM Ay

shall be a state variable if and

(1.6)

Ax

Whether a function is a state function or not can thus be established by relating it with two other known state functions through the above relationship and if it cornes out to be true it shall be a state function.

1.9

THERMODYNAMIC EQUILTBRIUM

This is very important concept for understanding the usefulness of thermodynamic science and its applications. This can be readily understood with the help of common examples. Let us imagine a inflated tube of an automobile vehicle. lf it is punctured in an open atmosphere the pressurised air from the tube leaks out through the puncture like
12

no extra pressure left inside the tube. What will happen if the same inffated pressure ? The tube is punctured in a chamber which has also been inflated to the same are equal l.e' since tube will not get deflated. since pressure inside the tube and outside a'pressure mechanical potentials on either side of the tube wall are the same' there exists chamber' or mechanieal equilibrium' in the system - the tube and its surrounding florvs Similarly if two objects at different temperatures are physically ioined heat lf the two were at the from the one at higher temperature to the one at lovrrer ternperature. equilibrium'' same temperature no heat flow shall occur. lt is then said to be in 'thermal lf two phases are in contact such that a chemicalreaction takes place between rates of forward and the thern, but the two phases can be present in such a way that the
a jet till

there

is

called as in 'chemical backward reactions are exactly maiched then the system can be same in that case' be equilibrium. The chemical potentiais in both of these phases must the ,thermodynamic equilibrium' is thus that situation where the system is Complete The with respect to all such potentials like mechanical, therma!' chemical' etc'
in equilibrium

term equilibrium is applied to a system and not to a process' '1.9.1 Paltial Equilibrium two phases systern can be in a state of partiai equilibrium. lt only means that the mentioned above the of one involved in a system are in equilibrium with respect to any all of them at a time' parameters, thermal, chemical, etc. or a combination of these but not say a mixture of nitrogen and if a system contains a semi- permeable membrane separating it is likely that the partial hydrogen gases on one side and only hydrogen on the other, pr"."rru" of hydrogen on either side may be equal because of the membrane being of nitrogen being permeable to hydrogen but the total pressures may be different because the system has total impermeable through the membrane. lt may take ages before the system is not truely pressures equal on both the sides of the membrane. Strictly speaking using a thermodynamic system and hence not amenable for thermodynamic treatment of on either side the state variables because of the continuously changing composition 'scale the systern can be considered to be a membrane. Yet within a reasonable time

is partialequilibrium system and treated accordingly. The equilibrium in such a case be so ireated with negligible error inrrnlved in the calculations' und "un 1.10 REVERSIBLE AND IRREVERSIBLE PROCESSES and irreTherrnodynarnic processes can also be subdivided as reversible inrrclving a system but not to a versible processes.These terms are applied to a process system as such. change in the A process that can be reversed in its clirection by an infinitesimal is said to be a'reversible driving force i.e. change in one or more of the state variables pressure of the process' A classical example of this is the gas cylinder and a piston' lf the piston' the gas gas is say P atmospheres and if (P + dP) is exerted from outside on the the external pressure is (P-dP) then insicie the cylinder shall be compressed. However if
the gas shall expand' A classical chemical reaction like

A+B-C+
'13

direction by changing the superimposed emf. This is a typicar reversibre process. on the contrary a match stick when it burns, the process can not be reversed by changing one or the other parameters. once burnt, the stick 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 sotution or flow of electric current through a resistor and so on. Alr natural procqsses are most often irrerersibre changes.
lf the case of a gas-cylinder and a piston is taken as an experirnentattool, it can be shown that the work done in expanding the gas very slovrrly through a wrlume change V1 to Vz is giwn by

go in the backward or forward direction by changing one or more of the variables, then it is a reversible reaction. A Daniel cell has op"n circuit emf of 0.76 votts and if the circuit is closed then curent flows in the direction "n sf zinc to copper in the solution and copper to zinc in the electronic conductor, lf an opposite external emf is applied the current slowly decreases and is zero when exactly the same value of emf is superimposed on the cell in opposite direction. Any further increase now wollld make the current florru from copper to zinc in solution i.e. reverse. Such a process can be made to go in the desired
if can be made to

and that to get the system back to its original position is

w1-2 = fu' Pdv "v,

(1.4

wz-r =

[:,

dV

rVt

^Vz I

pav

(1.8)

lf the process is carried out not so slovvly then it can be.proved that the work done in similar expansion and contraction is less than that done when process the is capied out / slorrly. Hence
work (rerrersible)
work(irreversible)

This is so because in reality the pressure difference driving the system to do work is maximum in rewrsible state. Although this is a simplified picture
gas it holds true for

any

under isothermal conditions applicable to ideal working substance gas, solid or liquid under any conditions.

1.11 CONCLUDING REMARKS

The enormous industrial rnanufacturing activities required to sustain the present-day civilization requires equally enormous energy. The energy resources are limited. lt is therefore necessary to understand the scientific principles underlying energy requirentents in these manufacturing activitias so that the minimum energy inplt n12y bJachieveo. The thermodynamic laws and their applications contribute towards this understanding.The basic terms such as energy' system, process, state and path properties, reversible and irreversible rocqsses, extensive and intensive properties and so on are required to understand these thermodynamic laws and these are therefore covered in the present chapter and the details of the thermodynamic raws are covered in the foilornring chapters.
14

CHAPTER

First law of thermodynamics

internal energy, enthalpy and their derivatives
2.1
HTSTORTCAL

energy of any system is is nothing like measurable absolute state, There chosen standard on a arbitrarily dependent differences can be measured. A energy of a system, it is all relative. Thus only energy system may have huge amount of energy but in a given surrounding it will be possible to give out only a certain anrount of energy and that will be the energy exchange possible and itwillbe measuredonly in terms of theenergyso released.lnthe presentdiscussion and as is of no consequence, the kinetic energy and the mass as a form of energy in nuclear terms, are omitted, being constant in any process, unless otherwise stated. It was Runrford who first appreciated the conversion of work into heat in qualitative manner in 1798. This was more properly explained by H.Davy in 1799 by showing that ice melted when two ice blocks were rubbed against each other under vacuum. lt was howerrer Joule who established through his famous experiment, in an adiabatic enclosure, the
quantitative equivalence of work and heat as

As seen earlier, from the definition, the measurable

work :'-"-= heat Joule

or

, J

w
q

(2.l',)

lf both work and heat are expressed in the same units then

for

a cyclic process

the Jorm of work gets transformed lnto anotn" ,.r::'? It means energy as heat fully. This formbd the basis of the law of 'conservation of energy' which is the progenitor of the first law of thermodynamics. lt also means that it is just not possible to produce energy of any kind without dispensing an equivalent amount of energy of some other form. lt is therefore impossible to construct a'perpetual machine' which will do work perpetually without putting energy into it in any other form.

,nrl;rJin

2.2

FORMUUTION OF FTRST I-.AW OF THERMODYNAMICS

ln a gravitationalfield work done by a body as a result of its rnovements depends on its initial and final positions and not nn the path taken by the body between these two positions. Similarly the work done by a charged particle under the influence of electric field

depends on the potential difference between the two points, between which the particle mo\'s, rather than on the path taken. Thus the work done, in the abor,re, by a body in its morrements from state A to state B depends on the functions of states A and B and not on the path the body takes for its movements.

ofwhichtheworkisdone, hastobedefinedandis called the'internalenergy'ofihesystem denoted in the literature by either letters 'U' or'E'. Here it will be referred to as ,U,. ln an adiabatic system the work done by the system on the surroundings.shall be equal to the change in the internal energy of the system as
surroundings simultaneously accepts heat from the surroundings then the work done shall be equal to the change in the internal energy of the system as well as the surroundings. The change in the internal energy of the surrounding shall be equal to the heat exchanged. Hence

ln otherwords the work done by a body in an adiabatic enclosure when moved from its initial to final state involves the same amount of work and which is independent of the path followed for the change. The change in the internal state of the systern, as a consequence

Similarly

if a

AU = w
system while doing

(2.S)

work on

the

Q = AU'

(surr)

(2.4)

lf the system and the resenroir supplying heat are considered as a single system and if this is isolated adiabatically, ihen the work done by this combined system equals the change in the internalenergy of the combined system, or

w = (AU'_AU)
putting Eq.(2.4) into this gives

(2.51

w = _ AU +
or on an infinitesimalform

(2.6)

dU = Aq -0w

(2.6)

given by Eq.(2.6).

This isnothingbutmathematicalstatementofthe'First Law of Thermodynamics'. ln a generalised form it can be said that if dg amount of heat is supplied to a system and if it does work 6w on to the surroundings the change in the internal energy of the system is
INTERNAL ENERGY AS A STATE FUNCTION.

2.9

Let us go back to Fig.1.2. The system happens to be in a state A and undergoes a change to state B. Firstly it follows the path 1 and second time it follovvs the path 3. ln both the cases the system returns to its oiginalstate via path 2. ln these two independent cyclic processes the net change in energy is zero as the system returns back to its original state. This has to be. The heat exchanged and work done in each cycle will have to be equal. Even from Eq.(2.6) if energy change is zero q has to be equal to w.

Therefore heat exchanged and work done in each cycle can be equated as in Eq.
(2.21as

w+
and

w1

t4l3+ w

+ q1 qb+ q2
clz
16

(2.4
(2.8)

and
and

q2-W g2-w

= u,h-Cn = w-q

{2.e) (2.10)

hence for that matter for any path follcnared for a ryclic change with state A and state B

as initial and finalstates constant W as form in infinitesimal or when expressed

Therefore for any change the actualvalues of w and g shall depend upon the path follored but the difference shall always be the sarne rs long as states A and B as initial and final states remain the same. ln other words the differnece (g - wl shall not depend on the path, although individually both of them depend on the path folloved, but on the states A and B only and, therefore (q - ui shall be a'gtate function'. For U to be a state function the values (q - vt has to be zero for a cyclic process and which is the case in Eqs.(2.7) and (2.8). Internal energy ls therefore a state propefi. It reveals that the system is capable of absorbing heat from the sunounding and doing work on to the surrounding such that Eq.(2.6) holds true. lt is quite possible that the system rnay, ts a whole, resuh in positive or negative change in U depending upon the actual values of heat g received and the amount of work w done. Hence sum of all forns of energies exchanged by a systemwith the sunoundings is
equal lo the change in its intemal energy. lt can also be stated as that 'energy san not be created nor can it be destroyed'. This is one of the statetrpnts of the first larrr of thermodynanics. lt can also be stated as 'tfte total energy of a systecr rnd it* suffoundlngs shall be constant and that it may change lts lorms or rnay exchange between themselves'. The system is therefore capable of accepting energy in one form and deliver it in the sarne or different form and in the same or different amount. This is possible because the system is capable of acting as a'reservoir' of energy. The stored energy is nothing but the intemal energy ol the system referred above and il increases or decreases depending upon its interaction with the sunounding or changes within itself. The internal energy consists of all $pes of energy forms contained by the system including mass if nuclear reactions are under consideration. ,As per Kelvin's definition thle presence o{ any particular form of energy will be seen only as a manifestation that the system produces, during its interaction with the sunoundirqs. For e:<arnple if nuclear

Aq - 0w =

con-stant

(2.11)

reactions are noi being considdred mass wlll not manlfest itrsetf m energy. Sirnihrly if electrical efiects are not considered electricalform of internal energy will not rnanifest. Jn chenical and metallurgical processes the thernral and mechanical energie alone manifest and therefore internal energy in those forns alone shalf be manifest and would be considered hereafter, unless otherwise stated specilically since chemical and rnetalfurgical thernrodynamic-s is being considered here.

the reader b conr,ersant with the terrns,volune, pressure and temperature as state properties and mw internal energy U has been added to this llst ol state properties to describe the energy content of the system. The question is whether there is any
So
frar

17

correlation between the directly measurable state propertiers like P,V and T and the newly
coined property U ?

lf the
where PdV

system expands by a volunre change dV against pressure P then the

mechanical work done by the system on

to

the sunoundings

isJ fOV and the Eq. (2.6)

shall

(2.',t2) be modified as : dU - dg - PdV - vl is the mechanicalwork and d is all otherforns of work like electrical, magnetic, surface, etc. ln normal chemical and metallurgical systens w'is almqst always zero because the system does only mechanicalwork and therefore henceforth w' is assurned to be zero, unless otherurise stated specifically. Therefore (2.13) dq -PdV It is desirable to have equation involving U the internal energy in the form where all quantities

dU -

are exact differentials, i.e. in terms of state properties. But this is the best first law of thermodynamics can lead to. This can be cast in the desired form only with the help of second lar of thermodynamias.

2.4

INTERNAL ENERGY IN TERMS OF PARTIAL DERIVATIVES

It has already been Sated that for a homogeneous system consisting of a given amount of substance of fixed composition the equation of state of that system can be (2.14') described as F (RVT) 0 gets automatically and since out of RV and T only two are independent variables, the third fixed and it can be described as

P=F(V.T)

The internal energy U being a state function will have to U F {RVT) is to say This also therefore can be stated as (like in Eq.2.15)

V- F(RT) and l=
=

FMP)

(2.15) (2.16)

be

a function of P, V and T and that

lf = F(P,V)t U= F[I,P) and ll =

FMT)

(2.1n

and fiom the theorem of partial derivatives dU can be expressed as

du =

(#)" dP .

(,ry),

dv

(2.18)

. (#), dr du = (,ry), dv . (#)" dr

du = (,+), dP

(2.1e)

(2.20)

and from these under the conditions of isothermal, isobaric or isochoric processes the dependenry of U on the state variables can be established. These equations in which
internal energy is expressed as a function of independent state variables are called 'caloric equatlons' of state as these allorrr evaluation of thermal capacities or heat capacities. For a single component system the caloric equation can be expressed also as

F F

(U'T,V)

(2.21)

and for mufti-component systern itwill be

(U,-T,Vn1

,nz,Il3,.....ni ) =0
18

I e.zt^l

2.5

HEATCAPACITY

ln any process, but more so in chemicaland metallurgical processe, materials get heated or cooled and therefore it is necessary to know the amount of heat required to heat or as a corrollary amount of heat liberated, in cooling a material, o\,er a certain temperature range. Different materials require different annunts of heat to get heated through the same temperature rise. This is because the materials have difierent heat capacities. 'This is so because of the variation in the crystal structure of nnterials and their related parameters.

The heat capacity of a substance is the amount of heat required to raise its temperature by one degree. ln a limiting case the same can be exprassed as

aq, cv = aT

e.z2)

The term specific heat refers to the heat capacity of unit mass of the material under consideration i.e. it is that heat required to raise the temperature of a mass of a gram of substance through one degree. Since g depends on path the value of heat capacity may also depend on path, if expressed in the form mentioned as above. ln an adiabatic process when g is zero the factor q \ dT becomes zero, which is absurd. lt is necessary therefore to express heat capacity in terrns of state functions. As internal energy is related to g and as it is also related to state functions,the heat capacity, through g could be related to state functions. lt should also be noted that the heat capacity depends on conditions of constancy of volume or pressure, particularly in the case of gasas, perhaps less so but definitely as well in the case of liquids and remotely so for solids as well. Hence two different heat capacities have been estimated, one as Cv as heat capacity at constant volunp and the other Cp as that at constant pressure.

2.5.1 Specific

Heat at Constant Volume

From first law of thermodynamics as in Eq.{2'13)

dU

or

= dq- PdV 0q= dU+ PdV

q

substituting in this the value of dU as given in Eq. (2'20)

o

= (,j#),

ou

. (#)" dr + pdv
'(#),+
!_e

= (#)u o'when

Pr

dV

(2.231

dV

0 under constant volume conditions

aq

= (#)"
or

dr

dr

q_

- /!_u\ lorju

ar

_ - /!l/\

lurju
(2.241

tr'V = dt

AU -]-=

Thus heat capacity under eonstant volume is nothing but rate of change of internal energy with temperature. The same thing can be arrived at in a differentway as follors : 19

Under the conditions of dV

hence w

or
or

0 no mechanical work is done by the system and PdV = 0 and hence from the first lal equation (d q)y = (du)v

(*",)" =
Cv

(#)"
as shown in Eq' (2'2a)
/ \

ls 2.5.2 Speclfic Heat at Constant Pressure lf pressure is maintained constant during change
final strte (f the work done will be

i --^ -^-r!^ conditions Ahhough g is a path fuhcticin heat exchanged under constant volume a state functton and equals change in internal energy'

= fH

of a system

from initial state (i) to

w= lrou '-- Ji
or on rearanging these ternrs

dv =PM-Vi) =Pf Ji
Q

The first larr equation as in Eq.(2'6) can be rewritten as

Ur-Ui = dq- PM-Vi) (Ur+ PVr)-Ui + PVi) =

The expression (u+ PV) is referred system and is ofien designated by the letter H as

to as 'heat content' or'enthalpy'

o{ the

fl= U+ PV H, = AH = H/ orthus bY dTwillgive

dividing

{12.251

dg

(2.26)

\d The heat capaclty at constant pressure ls nothing

fry) r/, lu

=f+) r/t or cp=#

.

(2.24

but rate of change of

enthalpy with temPeraturc' it in Eq' (2'13) as: The sarne can be derived using Eq.(2.19) and substituting dq= du+ Pdv

as dP= o
dividing by dT gires

(#r), dP + (#), o' dr ds - Pd/- f+) r/p

PdV

\d

u\ f4{) = c}D - - /d v\ /a l*,l'- lfrJ'

beingexactdifierentials
and

\d,/ dU= dU and dT=

cp =
(

dT

hence

substituting H lor U

[*#-],
PV) in the above
20

e'28\

cP

= (.+),

as in Eq.(2.27)

Altematively the sarne can be derived as: From the mathematical

definition of enthalpy difierentiating gives and since from first law hence and at constant prassure

f{= U+ PV dH=dU+PdV+VdP dq=du+Pdv dH= dg+ VdP since dP = 0 dH= dq

AH =
as

or

dg

as arrived in Eq.(2.26)

and by dividing this by dT Eq. {2.24

obtained.

Since enthalpy is a state function the heat exchanged by a system at constant pressure becomes a path independent property. ln other words it is a state proper$' Also by definition itsetf H depends on allthose parameters which are by thenrsblves state properties and it itsetf, in the derived form, is a state properS. Since enthalpy is a state property it can be expressed as a function of any two variables out of the three RV and T and thus expressing it as a function of P and T as

H(RT)=0 or
2.6

H=F(P'T)

(2.2e)

INTERNAL ENERGY vs ENTI'IALPY

One can readily understand the term lnternal energy as allthat energy stored in the system. But it is rather difficuh to understand the term enthalpy because it is defined by mathematical equation. Therefore what does enthalpy mean? This can be best
illustrated by the follcnruing example
:

Let us imagine the process of calcination of caleiurn carbonate Eiven as:

Heat is supplied to break the chemical bonds between CaO and COz . Assume for the tine being that both CaO and COz are solids. Then the invested bond energy would be internal energy of the process of calcination. ln this case the oniginal system of CaCOs with say conditions as P,V and T rernain practically the sarne after calcination. ltwould arnount to merely a solid/solid phase change. However if COz is allcnroed to form as gas in this process then on breakirtg of

CaC0s= Ca0+

COz

(2.30)

onegrammoleof CaCOe nearly 22.4lilres of CQ atSTPwillbe forrned as shown in Fig. 2.1. There is a tremendous increase in the volume of the system on calcinaiion. The system must do work of expansion to attain the nesultant expected system. The process is supposed to be carried out at one atnrcspheric pressure in norrnal atr;lospnere. lf the system has to attain a volume expansion of the order of 22.4 litnes at STP t['ben it should first attain a positive pressure against the ambient atmospheric pres$ure and then expand. ln this process of expansion, the system will do work equivalent of J PdV as mechanical work on to the surrounding. F{Bnce in addition to the requlitement of energy for breaking the chemical bond of CaO - eOa , additionalenergy equivalent of JeaV witt
21

Fig.2'1

Work done bY the Process

I

of

V@LUfl4

l0
I

i:)l ,Tr
voluME'

calcinatian

of

CaCOz un'

rM
I

io l-l

'22'4tttet

,l 6ry5 6Ts4Oi tPRE9CURE

oF ,e% ".1:---

16*eono" i N

:i: -L i-='tg6.MoLe CoeOg

HSAT.D

lot I
T G.

OFr

I eFrpru r-,---I--

ir^..", iCOl G'Ag

der arnbient Pressures of 1 amos and 10-3 atnos 4t two different calcination temperstures. Note the volutne
change after the reactinn-

7o

9Oo c

MOLE

HEATED

To

O*CO9 " 660-c

and this this process making a total of u + PdV energy have to be supplied to the systern for U' energy internal on calcination, quite difierent from the is the enthalpy change of the system

Forchemicalprocesseswherethereisnoperceptiblechangeinvolumeasin 2CaOs. SiO2 = 2CaO + SiOz U and H are almost the same' The difference tneJeUV term is practically absent and hence gaseous component in the system'lf there is no in U and H arises because of gaseous will be phases are piesent as in the equation above'there component and only condensed condensed phase changes to another condense<l no difference between U and H. When btt or can be negtgcteo orJeav term shall phase, the change in volurrre is negligible tor Jeov arises only because of gaseouii treated as zero. The perceptible value H' hence ih" diff"r"nce in values of U and component inrnlved in the reaction and, from this may have enthalpy alsc ' A system thus has internal energy and as distinct enthalpy is often more relevant 6nrj ln chemical ano mJallurgical world therefore the Even if the term Jnov isabsentitisworthwhilir distinctly different from internal energy. torefertoHandforgetabouttherealityasittakesintoaccountwhatitshould. Theusageofenthalpychangesasameasuringparameterisobviouslymoti: appropriatetotakeintoaccounttheworktermoftheprocessratherthanmereinternrll energy in chemic :tl thus very popular rather than internal energy. The usage of enthalpy is of her' :[he term ,heat oi reaction' is restricted to the exchange and metallurgical world. l' does not take into account the mechanicalwo during a chemical reaction and which
term associated with it as explained above'

2.7 |NTERREI-AT|ONSHIP of Cp and Cv

Fromthefirstlawolthermodynamicsatconstantpressuredq=dU+PdV
given in Eq'(2'20) and substituting the value ol dU as

gives

dq = (ut#), ou

(ruY)"'
22

ot +

PdV

and dividing by dT gives

# = (#), (,+) . (#)"

\fr,,|u

assuming constant pressure conditions

/e1\ = cp and f-a u\

it will reduce down to

lfrh

= ./v

=
ideal gas the rate of change

(#),

[(,+),

. e]

of internal energy with volurne at constant temperature For an is nil. That is for an idealgasbecause of its non-interactive nature.

l-l
la

v/r

=U

Hence
(2.31)

cp

- cv =
PV =
ylT
RT

(#), ,

or

For

idealgas therefore
1

(when V changes with and

= R/p obviously P gets fixed up)

dvidT
in Eq. (2.3.1) gives (2'321

= R/P and substuting Cp-Cv= R

2.8

CONSEQUENCES OF FIRST LAW OF THERMODYNAMICS The system

ln the light of first law of thermodynamics various thermodynamic processes can be studied to derir,e additionalrelationships.
studied is ideal gas and for which

PV = RT and (AU/OV) =
Process

2.8.1 lsothermal

The process is carried out when dT =0. The heat supplied to the system in this case must fully come out in the form of work done on to the surrounding. Hence

Aq

= 0w or

dU

=0
drnV

(2.33)

It is also true that in this case

6q= 0w= { pdv=/v'Tou'=*t{] +=*t{]

Similarly

'

(2.33a)

AH= aU+ /ev

= AU +

(PrVr

PiVi)

23

= AU + R(Tr Tf - Ti = Al'{ = 0

Tt)

(2.341

Since there is no tenrperature change

0 and combining with Eq. (2.33)

(2.34a1

Hence in an isothermal process both internalenergy and enthalpy rernain unchanged and work is done by the system equivalent to the heat input. Therefore now for an isothermal 0 and reversible work done by the O but dU = 0 and dH proqess not only dT

system is

!t/

= RT ln M/Vi)

(2.35)

2.82

lsochorlc Procesr

Under constant volume conditions the system does no mechanical work on the surrounding and henceJPdV equals zero. The first law Eq' (2.13) gets reduced to
and also

dU= dq 65=dU + PdV=-dq

(2.36)

(2sn

ln otherwords the heat absorbed or rejected bythe system during the process equals the change in the internal energy or enthalpy of the system. Therefore for a constant volume and also dU = dH = dq process dV = 0

2.8.g Adiabatic
dq

Process

There is no exchange of heat between the system and the surrounding i.e'
PdV dU=-dw= dU = CvdT = - PdV For an ideal gas fl= U + PV definition Also since by dFl= dU+ PdV + VdP therefore and combining with Eq. (2.38) dH = VdP

= 0.

Hence first

lar

takes the form

(2.38) (2.3e)

That the system does work at the expense of its fi/n energy and therefore temperature of the system shall fall. Using these relationships for a adiabatic process the interrelation of P and V or P and T can be found as
constant for adiabatic process relationship the how now recall Where y is constant. The reader will of partial derivatives terms in was giwn earlier in Chapter 1, Section (1.7). Expressing dU as in Eq.(2.20)

PV = Constantand tt(?)

du
and

= (#)rou - (#)"ot = Pdv asds = Cv and

(au/aVr

for an ideal gas and also assuming Cv to be constant over a certain temperature range it Cv dT = - PdV leads to Adiabatic work done can be obtained by integration of Cv dT over Ti initial and Tt s
finaltemperature as

since

(au/dTlv

Adiabatic work done

= -Ci/(Tr-Ti
24

(2.4o1

andsince
adiabatic

dU = -w= -PdV energy change = Cv (Tt - Ti)

(2.41\

2..8.4

PolYtroPic Processes

Since the polytropic processes obey P\f = constant, the final expression of dU and dH accompanying the polytropic processes is quite complex because the mechanical work done isJnV and notJPdV. Since both P and V change during the process, the account work done by the system will have to be calculated taking changes in both into level. and this is quite complex and therefore, not introduced here at the beginner's

2.8.5 Throttling and Free Expanslon This is a irreversible process carried

heat exchange to occur in such expansion in volume'

out adiabatically as there is no chance for instantaneous process of drop in pressure and free

0, du = - dw and hence the system performs work at the expense if there is a iet of its oarn energy and therby the temperature of the system shall fall. Therefore the jet is lcruver than coming from a nozzle in an open atmosphere the fluid temperature in the temperature of the fluid fed to the jet.

since dq

2.8.6 Deviation of Real Gas from ldeality

The ideal gas equationcorrelatingRV and Tisapplicableforidealgases'lnreality actual volume the actual volume of gas is not the apparent one but, that minus the occupied by the gas particles (molecules). Hence clausius modified itto. e'42) b) = P (V gas as ,b' the particles of molecular the by occupied represents the volume where interaction of molecular because ideality such. The real behaviour is further deviated from and hence van der Waal further nrodified it to :

RT

This is known as van der Watl's Equation and it comes more closer to real three alternative obserwd behaviour of gases. This is a cubic equation for volurne with values.Whenallthethree values are real,gas can be liquified. The lowesttemperature gas will not at which this is possible is called the 'criticaltemperature' and abow which liquifaction when ones the be liquified. The relevant criticalvolume and critical pressure are willbe possible. Although the modified forrn of gas equation to correlate the obsenred behaviour
of real gasets, is not

x N-b) = Rr /p-4) v'l

P'42a1

direct consequence of the first law of thermodynamics' it is explained certain expressions as here to understand limitations of ideal gas and its use in deriving in Eq.(2.32) in the form of derivations from first larv of thermodynamics.

2.9

THERMOCHEMISTRY

occur with ln thefieldof chemicaland metallurgical processeschemical reactions making but nothing are or without mechanical work involvement. chemical reactions in the form of or breaking of chemical bonds (in sonre both nny occur)' Energy exists
25

these bonds (in terms of bond strength) and hence energy, most often heat, is required to breakthese bondsand conversely it is releasedif bonds are formed. Henceinchemical processes heat may be released or absorbed depending upon whether chemical bonds are formed or broken. lf both of these, making and breaking, occurtogether, then the net algebric sum of the bond energies shall be released or absorbed, as the case may be. ln a heterogeneous process in which gaseous phase is inrrclred the workterm may be substantial. Whereas in liquid- liquid or liquid-solid or solid-solid heterogeneous systens the volume change, ewn though finite, may be negligibly small to contribute any worthwhile
work factbr in the process. ln systems containing a gas phase, if a perceptible volume change occurs in the process the work term may be dominant. Besides the direct chemical reactions, energy exchanges are also associated with phase changes that may occur in the process e.g. solid to liquid or liquid to gas or vice versa, in any of the phases involved in the process, Phase transformations in solid state likd order-disorder or austenite-martensite transformations are also accompanied by heat

exchangesbutto asrnall extent. The processofformation of solutions or de-formation of solutions can contribute a substantial part of heat exchanges occurring in a chemical
process.

The field of thermochemistry is to study all the above mentioned heat exchanges during chemical or physico-chemical processes. Calorimeter is often used to study these in a laboratory.

2.g.1 Hess's

law - Corrollary of First l-aw

As the heat exchanged in a process is seen to be a path dependent property, the heat exchanged in chemical or metalfurgical processes might also be enoneously vieured as path dependent property. These processes are studied under either isobaric or isochoric conditions and as shown

aU =

in Eq'(2'2al and (2.271 x: dg (for isochoric) and dH - aq (for isobaric)

The heat changes in chemical processes.are not path dependent but are state functions only. This fact was realised,though not quite in the way as is understood today, by G.H.Hess in 1840. He suggested that the total heat exchanged in a chemical process ls the same lrrespective of whether the process occurs ln a direct single stage or through multiple stages. This is now known as Hess's Law. It is now considered as a corrollary of first law of thernndynamics. lf Hess's law

does not hold good then in a cyclic process when the foarard process is carried out in say directly one stage and the reverse in multistages then it will result in a net gain or loss of energy. This ought to be zero in a cyclic process and hence both should neutralise each otherinsuchawaythat the net amount is zero as per the first latnr ofthermodynamics. Hence the Hess's lzul is a corrollary of the first larrv of thernodynamics.

The larrv can be explained by an illustration such as reduction of iron oxide by carbon or carbon-monoxide gas. The reaction can be carried out in one stage as (2.4?) 3Fez Os + 3C = 2Fe + 3CO '
or alternatively in stages as
26

The total enthalphy change in both of these routes is exactly the same. This can be proved

and

3FezOs+ C = 2FesOn+ CO 2FesO++ 2C = 6FeO+ 2CO 6FeO + 6C = 6Fe + 6CO

12.44\

(2.45l. (2.461

thus:
The enthalpy change in reaction (2.4i]) i.e. single stage

is

gi\,n by

3Hco - 3Hc- Hr".o. and enthalpy change in reactions Q'a l b (2.46) are AH1z.aal = 2HFeooq + Hco - 3H5er9. - H6
AH1z.+s1

= -

2Hre

(2An
(2.48)
(2.4e1 (2.50)
follcnrving data at 25 C:

which on addition gives the same equation as inEq. Q'al Example : Calculate the enthalpy of forrnation of WC from the

+ 2Hco - 2Hresg. - 2Hc AHlz.my= 6Hre + 6l-lco - 6Hreo - 6Hc

IHp.+sy
6Hneo

(1) wC + z|
(21 C+
AHo

oz

Wos

Coz

Oa=COz
'z

-285800 caVg g
wos

mole

(3) w +'tloz Solution

AHo = -940950 cali

mole

and and is obtained by addition of equations 2 and 3 and subtracting from this, equation 1 as change enthalpy give the required the algebric summation of the AHo values

AHo = -195700cailgmole : WC is formed from C and Was W+ C- WC AHo= AHz+693 -AHr

: -;ff' ;r]ffl"*
2.10
HEAT CAPACITY CALCULATIONS

(-285800)

Heat capacity for any substance is not a fixed value. For the same material it changes subwith temperature and the way it changes with temperature varies considerably from stance to substance. The actual relationship has to be established experimentally. Howewl Fol certain empirical rules have been suggested and are used for approximate calculations' value o1 mono-atomic gases at high temperatures, the specific heat GV or Cp approaches a Petil and Dulong materials solid and for is close to 5/2R 312R. For diatomic gases ihe "a*e suggested that the molal heat capacity is equal to 3R i.e. 3 x 1.987 = 5'96 cal/de'

as Dulong and Petit'l-aw (1319). Einstein developed the n*"rory theory for calculation of heat capacity based on quantum theory with certain assumptions regarding the nature of crystal structure. This is known as 'Einstein's Theory ol Specific Heat of sotids'. This was found to be reasonably valid for high at lcnn temperature ranges but it failed to explain the observed values of specific heats
gree. This statement is known
27

temperatures. This has thus been modified by Debye, that belor a certain temperature, known as 'Debye's characteristic temperature' and , which varies from substance to substance, the specific heat is given by

cp or cv = . 234R 1T/0o)3 =
or Cp or
Gv cr l"

464.5

F/0o)3

(2.s1)

(2.s2)

where 0 o is the Debye's characteristictemperature. This is also known as Debye's

fp

Uaw

for lorry temperature heat capacities. The obsened values of specific heats of various materials at lorv temperatures show good agreenrent with the above equation. Since the variation of specific heat of any substance with temperature is a complex
relationship, after exhaustive experimentation empiricalrelationships have been developed for a number of elements and compounds in the form
and

Cp=a + bT *"1."_, Cv=a'+b'T+c"

(2.s3)
(2.54)

where a,b,c,a',.b'.andc'areall constants characteristic of thesubstance over a certain temperature range. lf data are not sufficient the final term may be omitted. Simplification
is also possible by trsing mean specific heat over a certain temperature range as defined as

Cp or Cv
substances,

(meanvralues) =

{'w
(Tr

(or9p)

Often tables are available giMng the values of

Tz) constants a, b and c for a large number of

(2.55)

2.10.1 Kopp Rule

Where specific heat values of compounds are

not

known from experimentation it

can be approximately evaluated by the use of 'Kopp Rule'suggested in 1864. lt says that the specific heat of a compound A B shall approxinntely be given by a formula as : Molar Sp. Heat of A" By = rsp.heat of A + y.sp. heat of B per g atom (2.56) This

is fairly reliable for ionic

compounds wherein the individual elements obey

Dulong and Petit's law.

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

mate values of specific heats frorn 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. This can be explained by two examples as:
Example 2.n
A certain slag contains 40oA CaO, 35% lf the specific heats given are:

SiOz and 25"/o Alz Os

- 0.01031 cal/gl0o/mole Si0z - 0.01498 --do--Alz 0s - 0.01906 --do---CaO

then the weighted sum of these values shall be

0.01031

x 0.40 + 0.01498 x 0.35 + 0.01906 x

28

0.25

0.0095 cayg/Oo /rnole for the slag under consideration'

Example 2.2

0.05582 cal/g/oo, what will lf the sp.heat of copper is 0.096671 and that of silwr is Ag? be the nalue of sp.heat of an alloy of 60% Cu and 4Oo/" The weighted sum shall be

= =

0.096671

0.6

0'05582

0'4

O.O77322 caVglOo

2.10.2 Varlatlon of Enthalpy with Temperaturc

of direct relevance in chen$cal or range or that which would be etolved on cooling is as it varies with temperature is metallurgical processes. The basic equation of enthalpy
(A H)P

The heat content or enthalpy required to heat

substance over a certain tenperature

= Jr,

Jz

CP dT

change in heating the material from Tt to T2 temperatures temperature. The "ninapy and Tz ' A varieties of such shall be equal to the area under the cune between Tt depending upon their nature' relationships would be observed for different substances

ArelationshipasshowninFig2.2canbedrawnfor^Hasitvarieswith

AH = Hz - H1 = [';,

(a

b'T

+ c'T-z)

dT

=(rz-rr)a+(rz-rr) brz+ c

(+

+)

(2s4

related to cp the Knowing the values of Tr and Tz and a, b, and c as constants like absolute enthalpy a relative enthalpy cnange can be calculated. since there is nothing H298o k as the base levelfor value is only calculated. lt is therefore custornery to assign as comparison and actualvalues of enthalpy changes

tabular form for ready are estimated from the specific heat data and are compiled in in the form of HzsEok data' reference for various pure elements and compounds at room temperature Nornally reactions are carried out with the reactants being temperature and then the to start with. The reactants may be heated to sorne elevated reaction occurs to produce the products'
the value of A Hzssox values of enthalpy change at eggo K can be evaluated knowing reactants and Products as (2'59) (D A Hzsao - A Hzeeo (AB) - A Hzsso G) - A Hzgeo

Hzs'ok-

Hzssok

(2.58)

ForareactionsaY

A+ B - AB

.-,-

the

canbe evaluated from-theknowledgeofAH2g8ok and inrolwd in the reaction knowing the values of specific heats of reactants and products Kirdhofi's larl as explained in the lolloling section'
tnageneratbedwaythevahrotAHzgsoK

29

I
o-

Fis.22'
Schematic v ariation of e nthalP of soliy' lrquid, and gas Phases

F z UJ
al'

for different materials'

-1

tt

TEMPERATURE

T7

be afeasiblepropoExample z 2.3 Formetallothermicreductionof solid oides to weight of the system' sition the enthalpy change required is around 600 cal/g Establishwhichoneofthefollowingreactionisaviableproposition? 1. SPbO + 2Al = Al2 03 + 3Pb . 2. 2PbO + Si = SiO2 + 2Pb 3. Fez Os + 2Al = 2Fe + Alz Os 4. 3ZnO + 2N = 37rr + Alz Os 5. 2MnO + Si = SiOz + 2Mn
Given for the solid reactants and products
:

2PbO

+ 4/3Al + 4l3Fe + 27:rr + 2Mn + Si +

= Oz = 02 = Q = oz= Oz =
02

2PbO 2l3Alz Oe 2l3Fez Os 2ZnO 2MnO SiO2

AHo = -

104500 cal/g/mole

AHo ' = - 256600 --doAHo = - 196000 --doAHo =-83000 --do-

AHo =-92000 -do-AHo = - 209000 --do-

therefore

2PbO+ 4l3Al = 2lgAlzOs + 2Pb

from Hess's law

AHo

-152100
30

AHo

= -152100 3PbO+ 2Al= AlzOs+ AHo = - 228150

3Pb

sp.heat/gofsystem=

- ry=

-315cal

where 723 isthe sum total of gram atoms of products or reactants' -iherefore even if pure oxide was reduced it would not be possible to carry this dead weight will reduction. tn fact in practice the oxide will be impure, that is additional and rnake it non-practical' be there, and the specific heat will still further decrease lnthe same way the others can be calculated andassqssedtofindwhichoneis lt will be observed that the reduction of iron oxide by aluminium will be

a feasible reaction.
Example

a \Ery {avourable one and that is the thermit process of welding.

: 2.4

iron is oxidised by Calculate the temperature rise when 0.01% P dissolved in molten process to make liquid calcium supply of oxygen and solid lime at 27o C during a steelmaking phosphate slag at 17500 K by a reaction :

4[P]tzsm
Given:

+ 5{02}gmo+ 6

<CaO>3ooo= 2(3Ca0'P2Os)tzsoo

AHr = - 58500 cal 1. {Pz} = zLPi 2. alslPzl + {Oz} = 215 <PzOs> AHz = - 15160 cal AHs = - 3600 cal 3. {Pz 05 } = < Pz Os> 4.6/5<CaO> + 2l5{-PzOs) = 215<CaO'PzOs> AHe = -405300ca1 5. mean sp.heat of olrygen gas, solid cao and molten iron are 0'255, 0'1 and 0'1
caildegree/g resPectivelY' 6 Heat of fusion of phosphate

= +

4000 caU mole

Solution:TheprocessistobecarriedoutasshowninFig.2.3. lary as follows to obtain The final reaction can be built up in stages using Hess's
the overallenthalPY change
:

2Fl = 1ez) 4lillPl = 215 {PzI 215{PzI + {Oz}= 215<PzOs> 45[P] + {Oz}300o = 215< Pz Os>
add to

AHr = + 58500 cals AHr = } 58500 x 215 =

234o,0

AHz=
AH

-15160ca1s
AHz

= AHr + = 8340 cals

215

this a H of the reaction 4 and add solid cao to it to give a/s[P] + {Oz} + 215 <CaO> = 2/5 < CaO'Pz Os>

AH = 8340-405300 x = - 153380 cals

31

g{E} * {QIoc*= t(80')

t(Co0}*t
(t

tI6

fl;
J"ll rlG
$tPl

t fli
{ll
'['

lu la l2

It

ili

{Q}.ro'*

tt Eq)

*'

* t(Coo)oo*=
&6C0.0'EG)

(gCaO'E$r)
+AHt

Fig.

23 - The physbal

mode of the reactinn of oxidatbn of phosphorus

ftom

molten iron to give molten phosphate. Algebrically account for heating and for nrelting of calcium phosphate.

of reactants o4ygen

gas and solid lime to 17500 K

These are

= Cp x dT x mass = 0.255 x 1450 x 32 = 11840 cal 0.1 x 1450x 56x 6/5 AH= 6/5<CaO>smo = 6/5<CaO>l7sooo = + 9744 cals AH (3CaO.PzOs) 215 = 21000 x Us and ?5<CaO.PzOs> = , = 1600 cals :
{Oz} smo

= {Oz}rzso

AH

All these will have to be met from the exothermic heat The net enthalpy change is therefore

to obtain the liquid product phosphate.

= -153380 + 11840 + = - 130636 ca|s

This enthalpy is erolved when (4/5) x adiabatically the temperature rise shall be

9744

1600

togetequivalentmolten phosphate. Whenl00gof meltistakenand0.0l gof Pis oxidised

31 = 24.8 g of P is oxidised

in mohen iron

AH
Vl -

Cp'

mass

rn^ AL ., Q.l x 1@x 4hx

1306

31

4a

5.2o C
Phase Change

2.10.3 Enthalpy Change during

When phase changes like solid to liquid or liquid to gas or vice versa or orderdisorder changes or solid state phase changes like austenite to ferrite andlor cementite occur, energy exchange is a must and hence the enthalpy changes in such processes are given by the corresponding latent heats of such processes.

32

During heating of a materiat (or eren cooling in rewrse) from say Tr to Tz temperature if a phase change occurs in between then the enthalpy change will be given by
Process enthalpy

change

AHoir' _

= 4:'

ce dr(phase 1)

^Hf

- f;, cpdr(phase2)
where

(2.60)

phase changes occur in the over all process by the addition of similar terms in between the temperatures Tr and Tz . For example if manganese is heated fiom b00o C to say 12500 C, the overall enthalpy change shall include the enthalpy changes accompanying the phase changes for the intermediate phase changes such as Mn (cr) to Mn (F) at7zoo C, Mn(p) to Mn (y) at 11000 c and Mn (y) to Mn (6) at 11360 c and therefore the enthalpy equation shall take form as belcnru ; aH = I Cp(Mnc,) dT+ AH(.r-F) +JCe(MnB) dT+ AH(p-y) + u3-993o

such

A Hlo is the enthalpy of the phase change taking place at temperature Tf which is in between the temperatures Tl and Te . This equation shall get extended if more then one

9930

993 -13230

+/Ce(Mnr)dT + AH(y-6) + f
1373-14090

13zgo K

Ce(Mno) dT

(2.61)

1409.oK

1409-15230 K

This evaluation of enthalpy as shown mathematically abore can also be depicted schenratically as shown in Fig.2.4. lt would be clear from both that this evaluation of enthalpy necassarily requires the knowledge of Cp values of all such substances (crystalforms) inwlred in the overall process. lt is also clearthat if enthalpy is known at sorne temperature then iis value at some higher temperature can be found out as

AHrr=Hrl+

t,

cpdr

(2.62)

and with appropriate changes in sign in this equation it can also be determined at a lqryer temperature as well. lt means knowing the value at some temperature on the graph in Flg.2.2 the remaining can be added to or subtracted from it.

2.11

KTRCHOFF,S LAW

tenperature n (final). The reaction can be carried out by the route ABCDF or ABEDF wherein the reaction occurs qt temperature Tr and Tz respectively. ln either case the
enthalpy change is the sanre. The total enthalpy change can be evaluated by knowing the enthalpy of heating from AtoB,thenenthalpyof reaction attemperature Tr and the enthalpyof heating of products to temperature Tf . This requires the knowledge of Ce values for reactants and products and also enthalpy change --f the reaction at Tr . Alternatively the sarne process can be carried out by heating the reactants to temperature Tz followed by reaction at temperature
33

This is the law which helps to evaluate enthalpy of a reaction at a temperature when il is known at some other temperature. The variation of enthalpies of reactants and products with temperature for a certain reaction are shown in Fig. 2.5. lnitially the reactants are at state A at temperature T; (initial) and the final products are at state F at

\;:+= i;i;; --; il;

Hr*H4'change
ph"ose

u--+

Dhase

change

^S+d Mn : : = ------ --

f+d

Mn

='n;7
f
I
ts

t4

og"

P*:f,
H o-

Mn

t q
rgrso

l____| P1'"
400

-:--

---7
I

z
t!

f-*'-lr-I pnase-change
Ht

^*{ --/o --;l

il

i
i
I

t I
I I I I

ac+F

'l

o-T,
2AO

ly"

)*ffinn'
60

{l^^,.
--+

I
I I

i
I

t
i I

lr

o 800 1000 1200

1400

TEMER ATURE

1600 9K

J1800

changes Fig.2.4 - Representation of enthalpy changes in rnanganese' rcmryrature range involving phase for This also needs the knowledge of ce values Tz and then heating of the products to Tt either ln Tz ' change of the reaction at temperature reactants and products and ine enthalpy

on heatingrnfinganese aver 4

final states are the same is the same s]nce the initial and the case the overall enthalpy change is zero and therefore process BCDEB the net enthirlpy change in both the cases. For a cyclic

dn1 + JB-C

Jz

CP(Prod)dT-

Hr,

ftt

cp

(react)

dr

O+
A Hra

D-E

E-B
Cp (reast)ldT

B-B
(2.63)

or
if it is shown

as [Cp

- a Hr' = f:, I Gp (prod) '- Cp (react)1 = A Ce (prod) _ orr,= 1],

lOp dr

aHr2

(2.641

Knowingthevaluesofspecificheatsforreactantsandproductsandenthalpy changeatsornetemperature[Ir)theenthalpychangeatsomeothertemperature(Tz)can becalculatedfromtheaboveequation.rn""itentnapyvalueisknownateitherTlorTz the change in the enthalpy the above equation' Alteinatively the other can be calculated from and Tz can be calculated as values between temperatures Tt

E --t"'

I
I

5 a
F

z rrt

at
TEI(PERATURE

-- into accountJhe changes in Fig.25 - Enthalp change during a reaction taking enthalpics of the reactants and the prodrcts with tetnperature.
aHr2-AH1 = aAH=/'
ACPdT
(2.65)

/q#) o'
I

of constant pressure The subscript p is to indicate that this is valid under conditions as perthe original equation used in thederMation' ThisbthestatenrentojKirchoff'slaw' Itmeans thatthe raieof changeof enthalpyof aprocessorareactionwlthtemperatur of producis and ls given by the difference of the specific heats at constant Pressure the reactants. The same crn be arrived at as cp (react) = (9*), and cp (prod) /aH\

= Acp

= [#,),
0H proa

by subtracting

AT and since the left hand side is the A H of the reaction

:-d Hre*t = cp(prod)

cp(reaa)

(H), -rcp
totalenthalpy change will

as shown in Eq. (2.65)

either by route ABGDF or ABEDF the lf the reaction is carried out under adaibatic conditions

be

given by either

35

+ { ,CedT
roactants

AH1 aHr

f"

Cp dT
Producl*

reaction

Jo cPdr +
reectants

- {

cpdr
Products

reaction

either ABCDE mass of the reactants and the products. Basically the reaction process is details required the or ABEDF and this includes the heating and reaction steps. Given of any such process the remaining unknown can be found out'

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

Example: 2.5

point temp) Calculate the enthalpy of vaporisation of Mn at 19000 K (sub- boiling normal their and of fusion at 12000 K(sub-melting point) when these values are known at liquid and gaseous boiling and melting points and when the specific heat values of solid,
Mn are known.

Solution

The process has to be imagined enthalpy change will be

to occur as shown in Fig'2'6' The overall

+ r1580 I
-1

=*

J 580
| Jt2oo

200

Cp dT(solid) + AHr (150!0 K)

Cp dT(liq)

AHf (12ooo K)

which is equalto zero for a cylic process'

Hence
AHr (12@o

)K = Jlzm

-1560

ce dT(solid) + A Hr (15600 O

-fi:

Gp dT {liq)

(1200oK) can be All the values on the right side are known as given and hence AHr give the value of AHv (1900oR calculated. Similar exercise carried out for vaporisation can

2.T{

-r'

ADIABATI C FI.AM E TE

MPE

RATU

vo.-

that can be lt is often advisable to know the maximum temperature of the flame be calculated assuming achieved theoretically when fuel is burned. This is possible to in the combustion conditions of burning. lt means that whatever heat is liberated
adiabatic

ofwhateverconstituents (C,H,etc.)thatarepresentshallbeavailabletoraisethetemperature values for CO' COz ' HzO' of the products that make the flame' lt also requires that the Cp
is the enthalpy of the overall etc. be known for that temperature range. lf it is assumed that AH process Products at Tz burning "* Reactants at Tt .*

andif and

from the composition of are the combustion reactions then the products can be ascertained And the fuel and amount of air and or olygen supplied for its burning. Jr -Cp (Hzo) 'nxro + aH = f [Ce (coz)'nco, +
J2g8"K

C + Oz = 2H + oz =

COz HzO

"

CP

(oz).no,

+
36

CP (N2)'nNJ dT

S ol Ldn/n ( rs Bo"x,
A I lF t

#ffH0fo*

iluid
( cl

Mn

rd

I' u
+

fi

c,

o n o
U

l{ J F

Soltd.'Mn
S?ART
HERE PROCess

(soooK)

PHASC CHANqE

_AH4

(raoo-n)

a,oil*.{l

Fig.2.6 - Imaginary scheme of carrying out obtqin the desired end prodrct
similarly nitrogen term willappear only
7g:21.

the process to

The excess oxygen term will appear only if excess oxygen or air is supplied and The above will have to
air is supplied for combustion and in proportion to be integrated to obtain the unknown T as the adiabatic

if

llanne temperature.

2.13

CONCLUDIT.IG REMARKS

1. 2, g.

ential direction rather than for either direction to be equally possible. This limitation shall be dealt with in the lollowing chapter. This anormly, though not conceived in the first law of thermodynamics, can bei explained only in terms of the second law of thermodynamics. This will be discussed in

4.

Energy cannot be created nor can it be destroyed, it changes only its form' Energy can be interconverted. Although the first law as such does not impose any limitation on such interconr,ersion and,as is observed in practice, that mechanical work can be fully convrented 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. There is a certain tendency for the conversion of energy to occur in sone prefer-

the

follo,ving chapter.

37

CHAPTER

ondLawOfThermod namlcs entropy and its derivatives

3.1

INTRODUCTTON

unless acted upon A thermodynamic system in equilibrium shall stay in equilibrium equilibrium pasition' However if the by external constraints to make it move away from the the equilibrium state' systens' which system is away irom equilibriurn it willtend to achieve towards equilibrium and such processes are away from equilibriurn, upon initiation, shall move processes' Examples are are referred to as 'natural' or'spontaneous' or'irreversible' 'contact with) or depressurisation of an inflated heat flow from a hotter to a polder body (in under gravity and so on' The tube in a low pressure sunoundings or a free fall state is possible because in the spontaneous change lrom an existing state to an equilibrium potential and which is the driving force existing state the system happens !o be at higher thermalpotential and which forthe changeto occur. Highertemperature istherefore a higher higherpressureisa higher makesheatflowfrom higher to a lowertemperature. sirnilarly mechanical Potentialand so on. reverse direction in the lf a system is in equilibrium and if it is to be moved in the or non'sporilaneous processes' Thereabove examples, it would be termed as 'unnatural' in the form of mctor-pump fore water cannot be raised to an overhead tank unless energy, colder heatwillnotflowfrorna setisprovidedtothesystem from thesurroundings. similarly as energy to a hotter body unless aided by the surroundings in the form of compressor processes observed but in chemical in a refrigerator. These are the examples that can be naiural process or an unnaturalprocess' it is not readily possible to assess as to what is a state of the system' This can only be evaluated fr6m the knowledge of equilibrium can only The knowledge of equilibrium co/coz ratio in contact with Fe or FeO providing by oxide iron of guide us as to how to prevent oxidation of iron or effect reduction

a suitableco/cozgas mixture as surroundings. Thefirst law ofthermodynamiasmerely lt also

direction in which this will occur' states the inter-convlrsion of heat and work but not the potential to make a process take does not give any indication of internal energy being a of driving the process in place. The second law is able to devise- a potential term capable

the brm of a force' energy is fully The lirst law is based on the essential observation that mechanical it passible to carry out this process converted to heat(from Joule's adiabatic experimen$. ls

energy?' This was of in the re\rse direction i.e. heat to be converted fully to mechanical in the early days and also to direct relevance to understand the working of steam engines the performance of steam improre upon their efficiencies. These efforts to appreciate to the formulation of second engines in the 18th and 19th century ultimately led

lar

of therrnodYnarnics.
It would be worthwhile to

study an ldeal gas engine producing work by taking heat of such an engine' lt takes heat from a reservoir. Fig. 3.1 shows the P-V relationship A to state B doing mechanical from the surrounding and expands isothernnlly from state

worxequatof pV.lnordertorun it as anengine this must be done repetitively

to

The systern therefore must return produce work by taking heat from the surroundings' adiabatic comPression. ory back to A, its originalstatg.This is not po!9ible

t
I

el
z o gE l. tt kc' io.

I'OTHgiFIAL

ld

AT TE&iP :Tt

,{

t
I

E f

sl
0(

o (r)

c o-

ld

3n 6l'

<ct compn?gstoN
I3O'THERIfiAL

0( o-

lrl

(a)

E-

VOLUME+ (b)

related to a gas Fig. 3.1 - Typbat P-V diagrams in cyclic processes (b) shows a four stage cycle' engine ; (a) shows a three stage cycle and
in Fig'3'1 as processes BC and the gas system to its original state A. These are shown cune AB' The work cA. Both of these will have to be on the lcnryer side of the isothermal c*cF PV to leave out net I f"^ PV together must be and is less than lo J6 PV anO rc process" nnechanicalwork done by the system in a cyclic the gas ln such a ryclic process involving minimum three difierent processes and expands to do work' on rerrerse side takes heat at a temperature Tr from the surrounding the equivalent heat to the surrounding' and it has to isothermally compress first, desorbing it further to attain the original state A. This necessitates that then to adiabatically "o*pio" at-af?fperaturelower the systemmust.gire out heat duringthe isothermal compression work by expansion' The adiabatic comprassion than at which it earlier accepted it for doing the the original state A ls achieved' This whole shall raise the temperature to Tt again when 39

At lea$ two reversible

to revert processes, one of which may be isotherrnal, are needed

process, for conversion of heat to work necessarily produces a permanent change in the second surrounding reservoir by way of release of heat into it. This inevitable tnansfer of heat to the surrounding at a lower temperature, which is a permanent change in the second surrounding, to carry out the conversion of heat to work is called by sone as 'comlpensation'. Hence heat can not be converted to work without such compensation. dt also means that the entire heat that is absorbed initially is not converted into usefulwork but a part of it is rejected to the second reservoir as of necessi$. ln other words 'ln a cye8lc process it is

lust not possible to convert all heat into mechanical work, although 8t is possible to conveil all work into heat'. lnanon-cyclicprocessitmaybepossibleto convert all heat into work but in a cyclic process it is not so. The important congideration is therefore that in a cyclic process all heat can not be converted into work fully. lf heat is to flow from a relatirely colder to a hotter body, it is only possible by attaching the colder body to a gas engine which will receive heat from the colder body by way of its expansion and by adiabatic compression raise its ternperature to that higher than the hotter body and thus desorb heat taken from colder body to a hotter body. The work done by he gas engine as surrounding is the required compensation. The second lary assuned the form in the early days in the wonds of Carnot as'it is not possible to construct a cyclic devlce to convert heat into work fully on its own'. The same thing was put by Kelvin as 'it is iust not possible to con\rert heat into work ln a cyclie process without compensation'. A later version of second law by Clausius states that,'in a cyclic process it is imposible to transfer heat frorn a colder to a hotter body without producing permanent changes or cornpernsation in the surroundtng'. Max Plank suggested that'it is irnpossible to construct a eyclic device extracting heat from a reservoir and produce thermal effects elsewhere' (compensation).
The first larrrr states that a system is a energy reservoir and hence can accept energy in any form from the surroundings and give it out in the san or other energy forms in the same or different anpunt. ln the above example the system ( in the form of ideal gas engine and piston) accepts heat fiom surroundings but does not convert it all to mechanicalwork. A part of this ene!'gy is converted to work and a part is parted off to another system at a lower temperature. ln other words in a closed cycle operation converting heat into work a part of the heat input has to be rejected to a colder reservoir. The efficiency of this engine is given by net work done on to the sunounding
heat supplied to the system

3.2

CARNOT CYCLE

ln order to work out the efficiency of a steam engine Carnot in 1824 imagined a cyclic operation consisting of two isothermal and two adiabatic, each with a expansion and a compression, thus totalling four stages in a certain way. This is.shown in Fig.3.2 and is known as'Carnot Cycle'. The operation of such an idealised gas engine can be imagined to start from any point. Let us say it starts from A. The engine with ideal gas as the working substance is initially at A at pressure Pl , volume Vr and temprature T1 conditions. lt is

put in contact with athermostat at temperatureTt andisallorvedto expand, takingheat

and doing work

lfi

on the surrounding. lt thus reaches B at corresponding state properties

A (PrvrTr)
I9OTHERMAL EXNilSION

llr

-ot

(itrr)
Fig.3.2
ErsNaroN
-arr1 Q,t o

I
rc

.AOIA6ATsE

ADIAlATIC

E
0t

) U,

Typical Carnot cycle

operation.

an

br o.

(qy+rr)O

+ol I
ISOTHSRMAL Gf{PtcSlror{

C(tYr

voLUME
as Pz

._F

,Vz and Tr remains the same, at the end of the isothermal process of expansion. Now the thermostat is removed and it is insulated and allowed to expand further

adiabatically to conditions Ps , Vs and Tz doing further work W on the surounding and thereby reaching position C. Now Tz has to be less than Tr because of loss of adiabatic

work from thesystemtothesurrounding. lt is now again put incontactwith athermostat at temperature Tz and isothermally compressed putting in work vra to achieve conditions Pc ,Yq and Tz at position D. ln this it gives out heat q to the reservoir because of work r,16 being put into it from the surrounding for compressing it from position C to D. The thermastat is now renpved at D and system is insulated and further compressed putting we into the system from the surrounding which would raise the temperature from Tz to Tr and pressure and volume to the original Pr and Vr and therby completing the cycle. On the whole the situation is as follows : The gas engine takes heat qr at Tr temperature and does work wt and rejects heat A at temperature Tz while receiving work vE . The two adiabatic processes, one of expan6ion and the other of compression nulli! each other as far as the net change is concemed. Also since it is closed cycle the net work done and the net heat absorbed are equal and hence net energy exchange is zero. Therefore the total work done can be equated to the total heat exchanged as folkxvs:
lsothermal work done during Vr to Vz and during Ve to V+ equals the heat exchanged during the same period as q and gz . Hence as per Eq.(2.33) in Section (2.8.1) the two isothermal work terms can be written as

qz ln order to obtain maximum work all operations are carried out rewrsibly.
RTr

ln(Vzffr) + RTz ln(V+rus

) =

q1

(3.1)

41

dU = -g/ = -PdV gives dU and since = CvdT and (RTM dV Cv dT for an and rearranging the terns it becornes

From first law putting g = 0 for an adiabatic process

CvdT

idealgas

=Cy
Tr

= -

PdV

dV

v=)

R'.7
=
Cv -E-

dT

integrating between the limits

and

Te

when

Vz expands to Vs
(3.2)

ln (Vz A/s

Cv _R . ln (Tz /Tr )
V+
Vn

Vz =
Vs
hence on

Tz\ / l-l \ Tt/

reananging Y Vr -

Vs
=

Va

(3.3)

Hence Eq. (3.1) reduces to or it and since

means

RTz ln (Vz l/r ) RTr ln (Vz l/e) q1 + Tz ) ln (Vz A/r R (Tr

) =

=
clz

q1

(3,4)

RTr ln(Vz therefore

or

(Tr

lr'r ) = gt or Qt lT'r = (qr/Tr) = q1 + q2 Tz) -

R ln (Vz

l/r

(3.5)

that is

Tr-Tz_q1-q2 ql Ir 1 -[fafrr) = 1+ (qtlql

(3.6)

or
lnotherwords

V*!-o rr 1z

(3.7)

0 ry

=o

as all the processes

in Carnot cycle are carried out rewrsibly.

The cyclic summation of qnvft being zero holds true for any substance in the Carnot cycle engine and also for its any state like solid; liquid or gas as there is no condition-precedent like this in arriving at the above relationship. Hence the property ch.vft is a fundamental property and being zero in a cyclic process, it must be a state
function and not a path function. The grev , othenrise refened to as path function, denotes here only the actual anpunt of heat exchanged and the temperature at which it is exchanged. As was observed earlier while deducing the relationshigs lor Cv and dU and, Cp and dH that,the term qldT is also equi\ralent to dU under constant volume conditions and to dH under constant pressure condition and thereby become state functions, so also here, the term grevlT is a state function and is designated by the term 'entropy' and often

denoted by the letter'S' and hence,

r$dS= 0

or dS=

drev)

T
42

or

AS

qqev) _ -dT

(3.8)

efficiency of the camot engine The equation (3.6) in fact rneans the thernrodynamic by the engine operating as rnentioned above is in the instant case. The total work done into the system as q1 ' This fractor is nothing but cn + q2 and is divided by the heat input on the two temperature limits between which efficienry of the engine. lt oepenos solely efficiency is therefore independent of the engine operates. The thermodynamic engine only on the two temperatures' since Ta cannot be the working substance and depends

zerocentpercentconversionofheatintoworkisjustl:'tnoss|ble.lnotherwordsallheat heat
larr is-thus proved'Theconversionof cannot befullyconvertedintowork. Thesecond lwertemperature

at into work isaccompanied by the pernanentchangeinthereservoir

whereinapartoftheheatsuppliedbythemainhightemperatureresenoir,isdumped, and which is the required compensation'

3.3

ENTROPY CHANGE IN NATURAL PROCESSES

Allnaturalprocessesorirrewrsibleprocessesorthosewhicharearuayfrom in increase in entropy as will be obvious from equilibrium, when initiated they all result
the folorirring examPles

reservoir to a lcrt,trer Let us imagine that heat flovrrs froma highertemperatureTl temperature,o"*oi,Tzthroughaconductorundersteadystateconditions.The the reservoirs as surround-

in this instant case and conductor be considered as the system will be temperature gradient Tr to Tz across the ing. under steady state conditions there a system during the transfer of heat There is no change in the conductor as

conductor.

fromTtreservoirtoTzreservoir'TheconductorreceivesdlrentropyfromreserroiratTr -fz Tz ' Since Tt ' > and gives out entropy qflz to reseryoir at

i,-r,...^r heat is and gives out more' since the flor of and hence the system receives less entropy entropy' a natural process creates or generates a natural process the conclusion is that a hotter body is not possible as per The re\rse process of heat flovrr from a colder to just like that therefore entropy can not be decreased second laal of thermodynamics and it of an inflated tube can be cited' on puncturing' without compensation. Another example gets of entropy' Also the kinetic energy of a body gets deflated. The net change is increase means lt generated' by frictionalforces' wherein heat is frl"""" decreased, in of iceand ""iur.r " weight falls undergravitysayinamixture increaseof entropy. similarty if sorne impact' lt the and fall potentilt energy released by the water some ice is melted by the meansentropyoficeandwaterhasincreased'Thesameargumentcanthusbeputfor allnaturalprocessesthatentropyincreaseswhennaturalprocessesoccur. ltisdifficulttoobviouslyproveitinnaturalchemicalprocessesbutitisso. conditions' lf the cycle is carried out The carnot cycle operates under reversible the work done in each but, under irreversible conditions then
under identical state positions

+ '+

stageshallbelessthanthatdoneunderreversibleconditions'ltmeansthatthework and exchanged but less than heat exchanged done shall not be equal to the heat terms in invotveo in a carnot cycle the two work hence for a irneversible natural process
Eq.(3.1)'
43

Rr, rn (#)
therefore flnally leads to

Rrz

rn (":)

< (qr + qz

(3.e)

On processing these as was done earlier while deriving

the Camot

rycle this inequality

(3.10)

o>i(+eg > o
AS = or >
states
0

for Carnot cycle involving irreversible processes. For any isolated system therefore
depending upon whether the process is reversible

or

irreversible (natural).

This equation is the expression of universal la,rv of increase of entropy which the entropy of a system in isolation can never decrease'. lt means the isolated

system has to go towards npre randomness or chaos.

lf the argument is carried further and if the process is to be made to go like melting of ice or lifting of water into a overhead tank or reduction of oxides of baser elements and so on, then the entropy change is less than zero or dS < 0. ln all the above discussion the entropy change means total entropy of the system and the surroundings put together. These processes are all unnatural and hence it can be deducted that the entropy decreases
in unnatural processes.

For any given conditions of an isolated system there is only one and one true equilibrium state of the system and therefore the entropy law can be stated as that 'the conditions of a system in isolation can not be varied in such a way as to decrease

the entropy'.
lf a solid is melted into a liquid by supply of heat at the same temperature in the form
of latent heat of melting then where is this energy ? The temperature, pressure are the sane and the volurne is practically the same. For sure the minor change in volume accompanying the melting process can not account for the huge amount of latent heat supplied as work done. The internal energy is changed because of supply of heat and one may say that

dU = g (latentheat) -but such an equation hardly conveys anything beyond theappreciation

thermodynamics. The Carnot cycle states that the entropy of the system equivalent to

of firstlaw of
in

the latent heat has resulted in increase

Hfo Latent heat of fusion (3.11) ds Melting temperature Physically the rigid atomic arrangernent of solid has, on melting, become more flexible with more mobility for atoms/molecules, etc. ls entropy therefore a measure of this mobility ?

= MP =+ =

Thesaneargumentholds trueforliquidtovapour.transition atthe same temperature. Now the volume change and consequent mechanical work are not equivalent to latent heat of vaporisation. This is again a case of increase of entropy as Latent heat of vaporisation _ Hv _ g _ de (3.12) - B.P. - T boiling point The randomness of atoms/nplecules in vapour is far more than that in liquid. Therefore is

entropy a measure of randomness again ? The same argument can be put forth for mere
heating as well. Surely entropy is therefore a measure of randomness of atorns or molecules in the system. ln solid state, phase changes like crystal changes or order-disorder transformations and thelike occur, then the entropy change as a measure of randorness is more apparent. Since heat suply or heat evolution is an inelienable part of chemical and metallur-

gical processes, the associated entropy change in the sys-tem, us a consequence, is additional and more important parameter for study of energy changes during such
processes.

This can best be illustrated fromthe example of order- disorder change. The two structures one as ordered and. the other disordered are shown in Fig. 3.3. These.two arrangernents must have two different energies associated with them since the pres-

ORDERD
Fig.33 -

DISORDERED

The ordered and the disordered arrangements in a-solid

crys*I lattice.

The dnrk and the hollow circles represent two different types of atoms-

sure, volume and the temperature are all the sarne in both the cases. ln changing from one form to another sorne heat say g will have to be exchanged at say a temperature f K. This is based on the basic fundamental that two different systems with similar chemistry must have two difierent energies associated with them. lf the associated energies were

exactly the same thenthereisnoreasonforthemtobetwo difierent systems becauseP,V and T are all alike. The two therefore differ in only one form and that is the configurational

them. This energy difference can only be described in terms of its entropy alone which is different for different configurations and is described as qf[ i.e.

arrangerpnt of the atoms

dS, amount of energy.

in

3.4

COMBINED STATEMENT OF THE FIRSTAND THE SECOND tAW

lf a system is capable of doing only mechanicdl work the first lanv equation can be dU=dg-PdV put as given earlier as Eq.(2.6) as and although it is not exact differential equation it is all that first law can do. This equation holds true for a reversible process. The second law for a reversible process gives
45

dS=df
6t-,l

or

g=TdS

The two lavrrs therefore can lead to

(3'13) + PdV = TdS - PdV or 169 = dU lawsof thermodynamics' This isthecombinedstatementof thelirstandthesecond

Thiscombinedstatementincludesonlythoseterrrswhicharestatefunctionsandhencejs and the entropy' This relation is exact differential equation in terms of the internal energy on state properties only' therefore independent of path and depends
For irreversible processes second

lar

gives
(3.14)

used forfudher deductions'Areversible This is themqstusefulformandismostextensively equalitysigninthe above equation hencethe process isveryvery close toequilibrium and sign in one djrection indicates spontaneindicates equilibrium relationship. The inequality .ous or natural process as shown abow. By the same logic if (3'16) TdS < dU + PdV indicatesunnaturalprocessandenergywillhavetobeinvestedtomakeitgo.

ds>0 TdS>dU+ PdV or therefore gives On combining the Eqs (3.13) and (3'14) TdS > dU + Pdv

ri.1') \\

3.5VARIATIoNoFENTRoPYWITHTEMPERATURE(CoNSTANTvoLUME)
volume conditions as

Thisdependenryofentropyontemperaturecanbeevaluatedunderconstant follols : dS = EdI Second lal gives lar equation first putting vlaue of dqfrom

ds

(2.20) and using putting value of dU in terms of partial derivatives as given in Eq'

= # - i'ou

dU=CpdT
leadsto

os=Sar+
= = 0,

at constant volume dV

['.

(#),

+ 1

(3.17)

it reduces

to

(dS)v

Cv

and a finite

change (AS) =

T Jz Jr,

dT=CvdlnT
. CvdlnT
(3.18)

or
where

Sr, = Sr, *

Jrt

cv

d ln

(3'19)
:

do withheat exchangedbythesystem' By definitionitself entropyhassomethingto change has to be zero' Hence il aq = 0 then the entropy AtconstantrplumeconditionswhendV=0thefirstlaralequation

s1

Tr ' As a corrollary it can be deduced that is entropy at some reference temperature

or

dU

Ag

- PdV =t [fitju
/du\

reduces to

dU= dg=

TdS
(3.20)

or if dq is zero, there is no entropy change in the system then

or
exchange.

dU=-PdV

/du\

l,*,l.=-P

(3.21)

ln other words there can be conditions of constant entropy or so to say adiabatic condltions when the lnternal energy change ls equivalent to mechanlcal work

3.6

VARIATION OF ENTROPY WITH TEMPERATURE (CONSTANT PRESSURE)

Now putting

(ds)p
dg

dU + pdV = d(U + pV) =

= aqT

by definition
611

(ds)p=
or for a finite

(+)"= *(#; o'=

(AS)p

?o'

change

= -f: lr
Jz

Cp d tn T

or at sorne ternperature T2

Sr.= Sr,+ l'lr

CPdlnT
(3.221

sr2=sr'-4, ?.ot

Exarnple 3.1 : Calculate the entropy change when supercooled aluminium freezes at B00o K alongwith that in surroundings at the same temperature. Solutlon : The process can be imagined to occur as shown in chapter 2 as Fig. 2.6 The solution of this lequires the sp.heats of solid and liquid aluminium and Hr value for aluminium.The AH values are thus known and from this the entropy changes at various stages can be evaluated and then algebrically summated to get the entropy change in the system and the surroundings separately.

s.7
is

VARTATION OF ENTROPYW|TH VOLUME (TSOTHERMAL)

The mathematical proof for evaluating the variation of entropy with volume under isothermal conditions is considered unnecessary at this stage and hence only the finalform
given belor ; lf the therrnal volume coefficient of expansion is denoted as

o=

g (,+),
rry)

(3.23)

and similady the compressibility as

p=-1 r
then
dS
=

Iar/"

(3.24',)

ffou
47

(3.25)

As=
alternatively
Svz

t{
Sv, .

dv

(3.26)

* JVr [,

^Vz

dV

P.zn

the solution of this equation requires the knowledge of entropy value at sorne known volume as itwill not be zero

3.8

VARIATION OF ENTROPY WITH PRESSURE

It can also be shown that

ds=-(#),0'
or
3.9

(3,28) (3.2e)

dS=-crVdP
THERMODYNAMIC EOUATION OF STATE

It is possible to show that

P=r(,+)"-(#),
and also

(3.30) (3.31)

which correlate P,V and T and hence are referred to as additional thermodynamic equations
of state.

- '(#'),.

(#),

The mathematical derivations are omitted here as these are considered unnecessary at the introductory level of the subiect.

3.10 INTER RELATION OF CP AND Cv

It can be shown that Cp --

in the preVous section. where cr and p have the usual meaning This relation is useful particularly because cr and p are often known and it is rather easy to experimentally determine the values of Cp and hence knowing these Cv can be evaluated and likqivise the experimental data of cv and ce n|ay also be verified.

= f "u as described

(3.32)

3.11 ENAOPY CHANGES WITH PHASE TRANSFORMATION

The evaluation of changes in entropy values associated with phase transformations requires the knowledge of heat exchanges associated with these processes like, latent heat of fusion or vapourisation or sublimation, crystal transformation and so on.

: AS=+=# Vapourisation : AS=+=# Melting

SolidStateGhanges

: AS =

Hs

temp of transformation

generalised way the entropy change in heating solid iron from say 5O0o C to 16000 C can Ue evaluated by a complex equation involving all possible changes from 50Oo to 16000 C. lron undergoes transformation xs ct to p at 10330 K, p to y at 11830 K, y to 6 at

ln

16790 Kand mettingatlSl2o K.Theoverall equationgiving thetotal entropychangein this process is as follcnrs :
srazsoK =

4:' ?ot . nffij) - J:'; gry or * Al{1;Q r * * '1673

J''* r
1ozg

Cp (F)
J8O9

lz

ur *

J.,.r.

Or in a generalised form thG total entropy of a substance at

can be evaluated from a equation of the type
:

. ffi; +-) dr

P**

{ftc

(3.33)
.

a certain higher temPerature

9+Odr*+*f As=Aszss"*fn 'J2ga lr ,T, I

9#E)or* andsoon
I

(3.34)

till the temperature under consideration is reached.This is graphically shown in Fig. 3.4. in a schematic manner and the solution of which needs the knowledge of entropy value

22.60

p.zz

-bE

8y;;1;

r:

3 o =

I I I I I

ils
(-)
fa

*.gs 6J3 --

I'Y
o.'F
o

o'rai
-t

slreg

I
t I t I
I

tt."o1'j:
{.
55 -+ ----

iro o
g
F

lcrlo!5 r r i lr ll rl tt I

I
t I I

t!

Ir l1
al It lt ,l r1 ll ll tl

I
I
1

6 298 @
50 0

I I I t

irosfi 1185
1000

I I Ol I L6 73.,

$Lf

fEMPERATUR-E

oK + 1500
oC

to above its melting on heating iron from 25 o29eoK is nken as 6-5 calldeglmole. Note the absence of lilrcar point. TheS relati.onship between temperature artd the entropy values although it has
been asswned to be so in

plotting

this relationship'

49

at 2980K(25o C). These values areavailable asASzssoK (liketheearlierASzs"inconpriled

form).

Example:3.2
Calculate the change in entropy when 2 Kg of solid silver at 4O0o C is added to already molten 5 Kg of silrrer at 1100o C.Find out the entropy change in the process.

Given

Ce Solutlon

The solution of this requires that first the final ternperature of the total mass of seven Kg of silr,er is determined. For this the process of mixing of the two has to be imagined as shown in Fig. 3.5.. lt means that first (AHr + AHz + AHg ) shall be released to the silver comes down to 4000 C temperature. Then the

= 5 cailoo /mole (liq) = 7'3 --doHt (Ag) = 2690 cafmole at 9600 C (m.p.)
CP (solid)

F r

960'c

KG _A3(

F z u,

7 J o o ()

Fig,

35 - Shows the imaginary route of carrying out

the

thermodynamic process to abtain desired result.

mixing is carried out without any enthalpy change. The mass is now 7 K!. Whatever enthalpy was earlier giren to the surrounding is now pumped back to the system. Since it is not certain as to what extent the heating will take place, the heating is carried oui in stages. First the mass is heated to the melting point 9600 C. lf the available enthalpy is not enough even to

heat upto this temperature, to whatewr temperature it is capable of heating shall be the final temperature. But if the enthalpy is surplus then the remaining is used to melt the silver. Depending upon the surplus the equivalent silverwill be melted while the other shall be still sslid. ln that case the finaltemperature shall be the nnlting point 9600 C'

50

then it will be used to But even after melting allthe mass of silver, enthalpy is still left these calculations require the superheat silver and the final temperature can be calculated. All of mefting and which are given' specific heat values of solid and liquid silver and its latent heat point then the amount Once the finaltenperature is found out and il it is the melting the of solid left will be calculated. Then the entropy changes can be evaluated knowing shall give the required value' enthalpy changes in each stage. Their algebric sunmation

i.rz ENTRopy cHANGE Assocl,ATED

For a reversible process if it looses heat to the sunoundings and entropy

its surrounding and gairs it looses entropy, amounting to the noted that the heat excfranged divided by the tenrperature. ln this process it mr'st be loss or gain of the sarne amount surrounding also takes p.* in the process in terrns of either obeyed' The net sum of the of entropy as the case tnay be for the first lar has to be therefore always zero 6 : entropy cfiange of the system and the surrounding is (3'35) AS (system) + AS (surrounding) = 0

wlrH PRocEssEs the system receives heat from

for a reversible Process.

lf the

process is irreversible or natural then in the light of Eq.(3.10) AS {sYstem)

+ AS (surrounding >

(3.36)

and conversely if the

reversible process is carried out

in

a sYstem isolated from the

surroundings then (3'34 0 AS (sYstem) change entroPY no exchange heat no is Also if the process is at equilibrium then since there will occur and hence (3.38) 0 AS {sYstem) the entropy change is given Now. if a system undegoes a change from Ato B then % an,

>

AS= Sa-SR

assuming certain restrictions of conditions' lf sa sa then as 0 or it means tfiat the system A

= change. a undergo lf se > sR then As >

=
way from Ato B'

is

at equilibrium and will not

0 and the procFs occurs 0

spontaneously or in a natural

Attematively if

by external energy source. All these conditions therefore entropies i;e. systqm pltts surroundings. Under certain

sl > sg then As <

non-equilibrium position

of

the second judge the to criterion a lar of thernndynamics provides in the iorm of entropy change,
equilibrium

and the process can not occur unless helped above equalities or inequalities are for the total values

or

in a

process'

3.13 ENTROPY CHANGES IN CHEMICAL PROCESSES entropy being extensive Like enthalpy change as predicted by the Hess s lar, Hess's larru' Therefore entropy change in energy state function, snalt Jso be subiect to the change' gii"n pro"""s is the sarne irrespective of the path follorued in bringing about

i.e, in one step or in multiple steps'

EntropyofanysubstancecanbeevaluatedasfromEq.(3'22).as
51

^S--

JT.,

fz

Cp'dT
T

have been established for available in tabular forms.

The change in entropy is often related to datum level of AS2eso values which a large number of elements and compounds and hence are

Hence
shallbe
AS8go"

Asr = Aszsao -

Therefore entropy change in a generalised reaction

4,

*.ot
-

(3.40)

A+B=C+D +

= AS(C) zge"

AS(D) 2eeo

AS(A) 2e6"

AS(B) ass"

lf the reaction is carried out at any other elevated temperature then, as was done while deriVng the Kirchofi's law for evaluation of enthalpy, the process can be imagined to take place at 298 K and the products raised to reach reaction temperature T or, reactants raised to temperature T and then reaction carried out. Therefore to the above if the entropy
of heating Therefore

is taken into acount the entropy of reaction can be calculated.

ASrr=lsr,*.f'f

ot

(3.41)

where ACp has the same meaning as given in Kirchoff's law. Example 3.3 : Calculate the entropy change for the reaction

FezOs+3C=ZFe+3CO
at 2980

K. Giren : The standard values of entropies at

Fe

29Bo K for various compounds are

21.4

cal/O /mole

At

2980 K

C Fe CO AS = = =

49.5
32.63

--do--do--do--

47.3

2Sre + 3Sco - 3Sc - SFe, os 65.26 + 141.9 - 148.5 - 21.4

37.26 cayOo /rnole
:

3.14

CONCLUDING REMARKS

It is not possible to con\,ert all heat into work without bringing some permanent change in the surroundings. Because of exchange of heat the system undergoes change in entropy - a measure of randomnbss of the system. Natural procssses occur with increase in entropy. The second law proMdes method of calculating only difierence in entropy of a system. The entropy change is an indication of direction of the change as to wether it is natural, unnatural or is at equilibrium. ls this the only parameterthat indicates the direction of a change? The answer is giren in the next chapter.

52

CHAPTER

Thermod namic Potentials free enerry and equilibrium crieteria

4.1

INTRODUCTION

A system by itseff, in isolated state, or in contact with surrou rcings shall stay in equilirbium unless acted upon it by some constraints, But if a systemtends to mcve, as a result of being not in equilibrium or as a result of external constraints, there must be a driving force making the system morrc from within itself or underthe applied constraints. This driving force is referred to as thermodynamic potential driving the system to change to a new state. ls this driving force or potentialthe same under all conditions of the system or itvaries from condition to condition ol the system ? ln this context as heat flows from higher to a lower temperature the 1ow is possible due to the higher thermal potential in the form of higher ternperature. Similarly the higher pressure is a driving mechanical potential. Also higher electricalvoltage more is driving the electrons under the influence of electrical potential as voltage' These are
tangible examples and can be understood more readily. However the question remains as to
to what is that potential, forcing a thermodynamic process' wherein energy exchange occurs, be relativeS will energy associated take place ? lt is easy to imagine that a system with higher when unstable as compared to the one wherein the associated energy is lower' ln otherwords a natural change occurs the system moves from a higher to a lower energy level or mo\,es potential from a higher to a lower thermodynamic potential. lt also means that energy is a potentialg driving the system for change to occur. lt also means that for equilibrium to exists the potential. of all the systems or sub-systems within it must be at the same

So far the internal energy, enthalpy and entropy have been eurlved as energy
paranreters but it is notyetknown as to whetherthese actsingly orin combination as potentials in driving a particular Process ? ln deriving various relationships from second law of thermodynamics entropy was seen to suggest that for a natural process it is more than zero l.e. + ve and therefore for a unnatural process it is less than zero i.e. - ve. Therefore for equilibrium to exist the entropy shall have to be the same for all the systems and sub-systems. existing together. But it must be noted here that for a natural change the system ntorrqs from a lower to a higher entropy

level and hence entropy can not be considered as driving force bringing about the change'
Can intemal energy and enthalpy quali! as potentials capable of driving the process towards equilibrium, if already at higher levels ? lf the internal energy and the enthalpy are potential terms then changes in them will have to be zero at equilibrium and these will har,e to decrease

for natural changes or irreversible processes and increase for unnatural processes' Let us therefore see if criteria can be erolved mathematically to eraluate what constitutes as thermodynamic potential or potentials and if so under what conditions ? 4.1.1 Potential Under Constant Volume and Constant Entropy Conditions These are peculiar conditions in as far as eonstant entropy is concerned, since
constant volurne processes are well known. The constancy of entropy i.e. isentropic condition

possible under adiabatic and no exchange of heat between the system and its surrounding is of the situation under consideration. The combined statement of the first and the second larrs thermodynamics as stated earlier in Eq'(3'13) that

isthatwheredS=0i.e.afi=0andsinceTisgenerallynotzero(excepttheextrernecase of absolute zero state) therefore dg will have to be zero. ln other words the process is

4g=Tds-Pdv
and putting dS = 0 and dV = 0 it reduces to

where

dU = 0 for reversible or equilibrium process and dU < 0 for natural or irreversible process and du > 0 for an unnatural process. This is based on the earlier obseruation that dS > 0 for natural and dS < 0 lor unnatural processes' The equilibrium for such a process under eonstant volume and constant entro'py conditions shallbe defined as dV = 0, dS = 0, Q = 0 and dU = 0

dU=0'

a higher to a and for a naturat procqss the internal energy will decrease i.e. will change from loryer level and for aunnatural process just the reverse' The internal energy thus fully qualifies to be called a potential under constant volurne under the and entropy conditions. lt also means that the equilibrium shall be characterised, therefore constant volume and entropy conditions, by highest possible entropy' As a eorrollary as expressed be cAn and the intema! energy must be afunction of entropy and volune

which on partial difierentiation shall give

u = F (S,V)

(4.1)

ou = (#)u ds +

(#), ou

(4.2)

second The intemal energy is also given by the combined statement of the first and 'on

lar,rrsas

comparison of Eq. (4.2) with this leads to

dU = TdS

PdV

(#)"=rand

T ln other words by specifying U as a function of S and V it is possible to evaluate of any other two and P and thereby describing the system fully. By exgressing u as a function possible, under the is as variable it will not be possible to describe all the variables, speclfication of U, as a function of .s and v. For exarnple by stating say

ffi,=

-P

{4.3)

s and T of the system. The reader in the beginning in should now understand why such peculiar conditions were assumed
it will not be possible to determine the rernaining properties

u = F (qv)

deriving the internal energy as a potential term'

Now that since internal encrgy as one of the forns of energies of a system can be related to all the vadables of the systern, any change in the propertis of the system can be directly conelated to the energy exchange and that is what is required.

From the combined staternent of the first and secondlaurs as dU = TdS - PdV it Le readily inferred that in a reversible isochoric process change in intemalenergy is given "an 14.41 by = oq = process when i.e. by the reversible heat exchange. Also in areversibie adiabatic or

Jcu rJos

ag = TdS = 0 or under isentropic conditions the change in internal energy is equal and opposite

of reversible work done on the system as

Jau=-eJov
4.1.2 Potential
Under Constant Pressure and Constant Entropy Conditions

(4.5)

Now therefore it should be clear that these conditions are so chosen such that the complete systemis describable. The conditions here are that dP = 0 and dS = 0' H=U+ PV Now therefore on dffierenciation

dH=dU+PdV+ dH=g+VdP
Atequilibriurnwhen dP

VdP

by putting in first larrr and second law equations

= TdS +

VdP
0

(4.6)

dH=0
ln a naturalprocess
and

= 0 and dS =
0

dH > O for a natural Process since TdS < 0 for an unnatural process dl-t > 0 for an unnatural Process dH >=<
0

since T dS >

So therefore on the whole

for unnatural, equilibrium and natural processes as the case may be. Therefore the term enthalpy qualifies as being calted a potential term under congtant pressure and entropy conditions. The enthalpy can therefore be described mathematically as
On partial differentiation the enthalpy change can be described as

H=F

(P,S)

dH

(#r)-o'. (,s),.'
and (#).
=u

g.n

Comparing this with already derir,ed equation (4.6)

(#u),

='

(4,8)

Again by expressing H as a function of P and S for any system the remaining variables T and V can be readily found out and thus the system gets completely described.

It is also clear from the equation (4.6) that for isobaric.processes_the change in enthalpyofaprocessisnothingbutretrersibleheatexchangesince dH = TdS = dgandfor

adiabatic processes when

g = TdS = 0 the
state.

change in enthalpy will be J VOe over the

pressure limits of initial and final

4.1.3 Potential

Under Constant Volume and ConstantTemperature Conditions

These are useful conditions under which many practical processes are canied out in the form of a fixed enclosure and a fixed temperature. These conditions mathematically are

as therefore or
and

dV=0

and dT=0

TdS = dU + PdV for a reversible isochoric process (dU - TdS) = 0

d(U-TS) =0 A=U_TS

Let us define a new mathematicalterm as

then and

dA = 0 for a reversible Process, dA < 0 foranaturalProcess dA > 0 for a unnatural Process'

This newly coined function A as defined by (U - TS) qualifies for being referred to as a potential term under constant volume and constant temperature conditions. Being a function of variables which are all state functions 'A must also be a state function. Expressingasbefore A = F(T,V) and by partial differentiation

oo =

Now therefore and since therefore

(,+)" dr + fi= U-TS

(,t),*

(4.e)

dA = dU - TdS - SdT TdS = dU + PdV dA = - SdT - PdV

(4'10)

and comparing the two leads to

As A

varies with T and V and if this is known then S and P of the system can be evaluated to describe the system fully. This function Awas first defined by Helmholtz and therefore is known as Helmholtz's Free Energy. From the definition of A it can be written after difierentiation as
and for a reversible process clrev = TdS and therefore Qrev = dU - dA According to the first law, dU = grev - wrev and hence ftev = dU + wtev comparing the two equations leads to

f4\ --s lur/u

and

($) =-p
\av/.

(4.11)

64 = dU - TdS

(at constant temperature)

from second laal

or

dA

dA=-wrev

wrev

Change in A during a process is given by

Wrev'

work That the change in Helmholtz free energy in a procass is equal to the amount of is done by the system on to thesurroundings or is equal to the amount of work the system therefore A is function possible). The work capable of doing (being rewrsible it is the maximum .work function'. lf the system is capable of doing mechanical work alone then also known as The loss in A the loss in mechanicalwork is equal to the change in Helmholtz's free energy. giren isothermal of a result as is equal to the maximum work the system is capable of doing change only' change and that being maximum, will have to be achier,ed through reversible as in Eq'(a'10) dA = - PdV - SdT From
it is clear that for isothermal processes

capable of doing on the or the change in free energy is given by maximum work the system is surroundings by way of rolume expansion. Also for isochoric processes and free energy change will be in terms of temperature variation

J on = - e.J

ov
of

g'12')

Jan=-s.Jar

the system'

4.1.4 potential

Under Constant Pressure and Constant Temperature Conditions metallurgical These are byfarthe mcst commonly adopted conditions in chemicaland

engineering Practices. dP=0 and dT=0. It means written as The combined statement of tlre first and second lzurs of thermodynamias can be

or

d(U + PV-TS) =

d(TS) = dU

d(PV)
0

(4.13)

Now let us define a new term mathenratically as and therefore obviously dG = 0 for reversible or process at equilibrium dS > 0 for natural Process and since U + PV-TS < O for natural process and hence

G=(U+PV-TS)

(4.14)

dG <
Conwrsely and obviouslY

0 0

for natural Process'

hence G also is a state iunction G is a variable of functions which are all state functions and Helmholtz function G is referred to as 'Gibb's Free Energy'as distinct from the function. This free energy. Now or putting value of

for being called as The potential term under constant pressure and constant temperature conditions'

for an unnatural Process The property or function G as defined above thus qualifies

dG >

=U+PV-TS { =U+PV AG =H_TS

G
AG

(4.15)

or for a finite change

or and at constant Pressure and hence

dG dP

=AH-TAS =dH_TdS-SdT =0 dH =9=TdS dG =-SdT

57

(#),--s
Again on putting
putting in
611

(4.16)

this

66 = dH - TdS - SdT = dU + PdV 66 = dU + PdV + VdP - TdS dU + PdV - TdS dG=TdS+ VdP-TdS-SdT" =VdP- SdT
0

SdT

or

{4.17)

at constant temPerature when dT = dG = vdP

or

/dG)

since G is a state function any change in G can be represented as

l*Jr

=V '

t4.18)

6Q=AU-TAS+ A(PV) - wrev + A(PV)

d(PV)

or for small changes

dG=-wrev*

(4.1e)

Therefore the change in Gibb's"free energy is equal to negative reversible work for obtainable from the thermodynamic process (as is Helmholtz free energy) but corrected the change in volume during the process i.e. corrected for mechanical work done during process. ln the definition itself it is so as would be obvious as

and

By adopting G

as a function of T and P as

G=U

A=U_TS -TS + PV
G=F
dG
(P,T)

(thePVtermisthecorrectionfactoQ'
(4.20)

on partial differentiation

(#),.r.
S

(#),

o,
as in Eq'

and on comparison

since

dG =

dT

+ V dP

(4'1f
(4.211

and f#) =V =-s f*'l \"-/r \drip

applies for others.

Since all are exact differentials dG in place of dG makes no change and the same two Thus by knowing G as a. function of T and P it is possible to establish other variables v2. S and V and obtainthe description of the system fully'
Example 4.1

Calculate the free energy change of-a reaction

<Si> + {Oz} -

<SiOz>

at a temperature 9000 K

Solution:

AGo$oo=AHogmo-1ASosoo, ='[AHozsa

- Jfl: 299

Ace

drl -

T[asozsa

*
where

9m

Jr*

Acq

J:

drl
(reaaans}

directly given or indirectly inforrnation is required either as Therefore to solve this tne tottoaring

AC = 2 CP Froduc{s) X Cp

calculable. _r^ ^-roroducts in the range of 29go (1) Cp values of individual reactants and

g00o K.

(2)AHoandASovalueslorallreactantsandproductsal2gs:..Kasstandardvalues' be obtained' be sotved and the XGosoo can *qtratlon llthese are available,n*it " above "tl G and their Extensive Natul and A H, U, 4.1.5 Functions
Allthesearemathematicallydefinedfunctionsandareinterrelatedtooneanotherand

toP,VTandSas

H=U_PV A=U_TS

G=U-TS+'PV=A+ PV =U+PV-TS=H-TS
Alltheseareusefultoevaluateenergyexchangesinthernrodynamicprocesses'Since

energyofasystemcanberelatedtoth*uu,i'bl""ofthesystem'anychangeintheproperties o{thesystemcandirectlybecorrelatedtotheenergyexchangeandthatiswhatisrequired' ltshouldalsobenotedthatoutofalltheseenergyparametersonlyGissuchthatitcanbe assessedintermsofallvariablessuchasP,V,T-andSatatime.ThefunctionAcanalsobe

similarlycorrelatedas-A=9-PV-TS,butitisnotexactdifferentialequation'The
functionsUandHarerelatabletoonlysomeoftrresefourvariables.Gisthereforebyfarthe procbsses mostexhaustiveenergytermthatcanaccountforvariedvariationsinasystem.Nowonderit in chemical and metallurgical the energy tolsess extensirely is used "t"n"ng"u physical whereinnotonlyP,VandTchangebutalsothechemistry.Allthesefourpropertiesare process involving chernical and/or

and are additive' no' extensive state properties "ny the free energies ol the two is given uy the difference in energy cr,angJ AH TAs changes tnu has occ.urred. Therefore 6Q = after-th" '; other so states, one before reference to a reference state' "no,n" shown to b" m"."rred with u""n and the H at s and since state' Hence like H and in reference to such a reference G also has to ue asslsea

f*"

;;";;;

sl.*

referencelevel ..^ +^ao AGo=AHo-TAS(

SimilarlytheHelmholtzlreeenergyAalsocanbgexpressedwithareferenceleve]. trom Systems 4.1.6 Availability of WorUEnergy

Howmuchenergyandinwhateverform,isextractablefromasystem?ltcannotbe in a well defined to, il from a well defined system once. fixed is it but any amount from the mean sea leve "no *rJ is jneters water that say us surroundings. Let ", " tvel :l ll andthehydro-electricgeneratorislocatedatMzmetersfromm.s.l.Theenergythatisavailable is equivalent of (Mr - Mz electric
to be converteJ to in the form of potentiai energy

?:**t

meters.FromthesamedamltgeneratorsarelocatedatMgwhichislessthanMzoratM.t bvelwhichismorethanM2leveltheatlailablepotentialfromtheSarTleresenrciriseithel
59

increased (at Ms ) or decreased (if at Ma ). This is also obvious fiom the definition of energy that it is not absolute but equivalent of effects it produces on the surroundings. lt is measured as a difference and upto the ler,el to which it can be lowered. lt can not be lowered below that of the surroundings.

Now let us irnagine a system at pressure Ps and temperature Ts in contact with

surroundings at P and system and

T.

Let us also assume that the system exchanges heat and work with

the surroundings. Let us assume that g amount of heat is given by the surroundings to the therefore q Now since

Ps AV) where work done is only the terms transposing By only. the surroundings on and mechanical (4.22) 0 AU-TsAS+PsAV=oI( The Gibb's free energy has been defined as above on the left hand side and hence from the

AU = g

= or < (TsAS) - v/ = or < (Ts AS -

above

AG = or < 0

This is the energy freely available in the form of heat and mechanicalwork from thesystemorits ,avaitability' (disregarding energy changes in all other forms). lt may be surprising to see that the energy available is a function of Ts and Ps and not P and T i.e. the functions of the surrounding conditions and not of the system itself' The inequality sign indicates non-reversible condition and the equality sign the reversible condition when maximum work will be carried out. Hence taking the equality for the change

putting

The term -TAS is the heat extracted from the system and can be gainfully converted to work through a Carnot engine operating between T and Ts temperatures.The work done by the Carnot engine would then be - (T - T=)AS. Similarly if the system is allcnrued to expand as AVthe mechanicalwork done by the system shall be effectively (P - Ps ) AV . Therefore the above equation (4.24) shows the free energy or the maximum work (energy in generalised

AG= AU-T"AS+ PsAV intheabove AU= q-w = TAS-PAV AG = TAS - TsAS - PDV + PsAV = (T - T") AS - (P - Ps) AV

(4.231

(4.24),

term) available from the sYstem. lf p = ps and T = Ts then no net work is available as AG = 0. The system is then in equilibrium with the surrounding and hence no exchange of energy is possible. The larger are (P - Ps ) and (T - Ts ) gaps the larger will be the the energy available from the system. ln chemical reactions when chemical bonds change, the energy exchange
is taken care of bY the term

TAS.

It is thus clear that maximum bnergy available from a system is not absolute but it is with reference to the conditions of surroundings. ln a gir,en surroundings AG gives the maximum exchange possible and hence very aptly named as free energy of the system'
ln the above example of hydroelectric generation the lewl of the dam is the surrounding, source of energy, and the level of the hydro-electric generator as the system. lf the temperature and the pressure of the surroundings are fixed the availability of a

given system is fixed.

60

4.2

PARTAL PROPERTIES AND CHEMICAL POTENTIAL It is easy to appreciate extensive properties like volume, internal energy, enthalpy,

entropy, free energy, etc. for pure substances in terms of unit mass or per mass mole (as molal propefi). But when the substance is in dissolved form r.e. in an homogeneous multicomponent system, what is its molal extensive property ? The answer is not simple. This can be understood by taking an example of volume for the purpose of illustration. This is chosen because it can

almost be 'seen'and thus readily understood.\Mten in solution the individual component

occupies the total volurne of the solution as its ovrrn volume irrespective of its concentration in solution. Can it then be said that the molalvolume of the component in solution is equalto the

solution volurne ? lf this is assumed then the molal volume is practically the same for all concentrations of all the components in solution. This is absurd' Similarly it is rather difficult to visualise the potentialterm driving a chemical reaction
between phases wherein more than one components are inrCIlred. The question as to which way a component would move between the two phases under a given set of conditions needs to be answered in the same way as answered above while deriving conditions for determining the potential term. Under the characteristic conditions of constancy of S and V internal energy acts as the potential driving the process.Under these constancy conditions does U become the potential term driving the chemical component from one to the other phase? Same argument can be made for H, A and G values also.The answer is not direct and is interlinked with the molal internal energy of that component in the multicomponent system. The molal property of a component in a multicomponent system thus needs to be properly understood. The problem is solred indirectly interms of thermodynamic concepts by coining a new term called 'padial quantity or property'. This is applicable to extensiw properties only. Let us imagine the components, solute and solvent, initially in separate vessels as shown in Fig 4.1(a). Each is one g. mole in mass. Let us imagine that the solute is transfened tothe solwnt but somehow kept separate as shown in Fig.4.1.(b). ln the next stepthe partition is renrcved and the two are allowed to get dissolved to form a homogeneous system - the

solution. lt is almost rare that the solution volume will be equal to the algebric sum of the componentvolumes. ln reality the solution volume is either less or more than the algebric sum of their molal component volumes as shown in Fig. a.1Q). lqw let us imagine that whatever

H H
(ol
61

Fig.4
The process of

.1 -

mixing of two

components to form a solu'

tion with some imaginary

steps.

be the individual sum total of the atomic or molar volunres of the components in solution, these

are somehow isolated in the form of two layers, the algebric sum being equal to that of the system tolume. Whaterrer is the individual component molalvolume, the molalvolume in the system is either less or rrore than that value when in pure forrn. This change is due to the interaction of the components when present together.The interaction originates from their different chemical nature,electronic structure and so on' Although the abore picture can not be construed in reality it can be evaluated by
mathematical formulations as follors
:

While deriving the thermodynamic potentialterrs it has already been shown that

U = F (S,V); H = F(S,P);A = F(T'V)

; and G =. F(T'P)

These are valid for systems of fixed composition and when characteristic two of the four variables P,VT and S are fixed. For example at constant T and P the system attains equilibrium at a minirnum value of G. But if composition is changed keeping T and P the same, being an erdensive property
the value of G gets changed and hence the system no longer remains in equilibrium. The sarne .arguments can be made for U, H and Avalues as per above equations. Hence strictly speaking if chemistry of the system is variable the above equations get modified as
:

U'=.F(S,V,nr,112,h3,....r...ni)
H' = F(S, P,nr,Il2,Il3,.. ! ! r..' ni) A'= F (T,Vnr,ll2,ll3'...!'..'ni ) G' = F (T, P,nr, Il2, ll3'., r..... ni)

(4'25)
(4.26)

$.2n
(4.28)

The prime on these functions is to indicate the overall property of the solution as distinct lrom that related to only one mole or atom. The folloning is illustrated for G only but the sarne treatrnent is valid for other properties like U, H and A'
Differentiation of Eq. (4.28) gives:

dG'

= -

(#)*",
/aG\
"""3,...

..

.dnr+ /aG\
ni

.dnz
ni

lFjr*nz,n3,.....

l*,,|rr,",,"3,...,.
dn'

.. .n,-, on the right hand side all other vanish' This terns two lf composition is fixed, except the first
equation can be simplified further as

- /aG\ |.fr,lrr",,n2,..
*

(4.2s1

dG' =

- sdr + VdP -

(fir0",,"".....n,-''

dn'

(4.30) in

ln this the last terms mean the rate of change of values of G' with changes

concetration of one component at a time. How is it possible to change concentration of one component in a system and yet not change that of the others in the system ?

62

of

This difficulty is orrercorne by irnagining a system large enough such that by addition one mole of a component I would not materially alter the composition of the other

conponents. The change AGr accompanying this one mole addition is thus the molal G value of as that component i in the rnulticomponent system. lt is expressed in the differentialform

/aG\

(4.31)
ni-1

l,6,lr.",,"".....

conponents. as the molal property of component i in the system consisting of several other putting a bar by denoted o{ten is This This is known as 'partial ProPefty of that component'. on the symbolas for exampleG called as G-bar or bar-G. Therefore

PartialmolalinternalenergyU
Partial

= f+)

(4'32)

\d^i]s,vn' nr,... .. ni-i

1aH\
(4.33)
....

molalenthalPY H =

lfrJr,*n,,",,n3.

ni-l
(4.34)

Partial rnolal Helmhol? free energy

A= (u*),,n",",,

n-1

and the partial nrolalGibb's free energy is as shown in Eq' (a'31) than one The total extensive property of a homogeneous system, comprised of more therby making component, consists of partial parts contributed by each one of the component, overall total to the component of a contribution the total property of the system. This individual of one mass total a for extensive property is called its 'partial property' and when expressed expresed gram mole or atom in the system becomes its 'partial molal property', and when property'.The molar is its 'partial for a fraction of the total one gram mole or atom of solution depends upon partial propefi is ordinarily differentfrom its pure phase property . The variation

the interaction between dissimilar components in the system.

AtconstantTandPthefreeenergyofasolutionwouldbe:

dG'=

\""'/n1,n4n3.....ni -l T lf the For a given composition with minimum G' the system shall be in equilibrium' values factual the concentration of one component is changed, obviously depending upon system shall gain The above' equation the given by either G' will decrease or increase as or with another equilibrium by allorting exchange of that component with the surroundings
1

i l,#)

= )aGi

{4.35)

ln other words the value sub-system till again thl original equilibrium composition is achieved' otei i. e. partiaimolarfree enprgy is acting as a potential in driving that chemical component Gi is thus the in a certain direction to achieve equilibrium. The partial molar free energy composition of the system. This is therefore designated as

potential in terms of chemical ichemical potential' and expressed commonly by the letter similarty for U, H and A it can be stated as :

in the literature. By arguirq

63

JUL =

/au\

l6jr,nn,
/aA\

n,,n,..

lfrJrnn,,n.,n..

lanijr,r"r,hz,ng.....hi -r /aG\ = l-l .. ni -r \dn'/tRn,,nan3..... ni -r

....i -r

_ - /!H\

{4.36)

or (Gi) tA $sn However each term shall act as chemical potential term under the conditions of constancy under which it acts as the thermodynamlc potential term. lt must therefore be understood that U is a characteristic function of independent variables S and V and composition and likewise others as discussed earlier.These can be written as :
1Ui)
I

or p =

or F'i) or

dU=TdS-PdV+
1

pi .dni
i

(4.3e)

dH=TdS+VdP+ 2.. T
1

U.i

.dni

(4.3e)

dA=-SdT-PdV +)
1

pi .dni
I

(4.40)

dG=-SdT+VdP+ ) Fi .dni Now since from first law dU=g-w

1

(4.4',t1

from Eq. (2.12)

therefore dU = TdS

= TdS-PdV-v/

PdV

[chemicalworkintheprocess(r+/)]

(4.421

ComparisonofEqs(4.38)and(a'a2)girethatchemicalworkis=>
1

it means that migration of chemical species over the available coordinate when multiplied by the driving force that is the chemical potential, pi in this case gives the chemical work done in the process by the migration of the chemical species. Partial molar energies as shown above are the driving chemical potentials. lf a two, phase multicomponent system exists, then the p;ghasel) = p;(phasen) for equilibrium to exist forcomponent r'. ln case these are not similarthen i will migrate from higherto a lorrer potential side.

Like all other potential terins the chemical potentials of a component in different phases in equilibrium or between system and its suirroundings or between sub-system of a system will have to be equal for the component to stay in equilibrium. lf il is unequal in that case the higher chemical potential shall drive the component from higher to a lower potential
zone. Likewise complete chemicalequilibrium shall be possible only if chemical potentials

for all components are correspondingly the same in all zones of the system. Transfer of

chenrical species from a zone of a higher potential to a lorer potential shall be a natural process and vice versa as a unnatural process. Most of the chenical and metallurgical processes are carried out under constant tenperature and pressure and therefore partial molar free energy 6i is commonly used as chemical potential term to Fsess chemical equilibria.

4.2.1 Maxwell's Relations

We have derived

as in Eq.(4.17) All these are exact differential equations. From the propefi of exact differentials the follaling relationships can be stated

dU = TdS - PdV dH = TdS + VdP dA = - SdT - PdV dG = - SdT + VdP

as in Eq.(3.13) as in Eq.(4.6) as in Eq.(a.10)

(#), = - (g)"
(,+). = - (,+), (*^), = - (#)"

(4.431

(4.44)

(4.45)

/\ = _ rcy\
\aP/,

(4.461

\ar/,

These are popularly known as 'Maxwell's relations and are usefulfor calculations of thermodynamic pararneters. There are four variables viz. RVT and S and the variation of one with the other is related to the variation of the third with the fourth variable under certain conditions, in the serelationships. Thermodynamic Mnemonlc square is available to anive

atthese relationships by a thumb rule. These equations apply to any system which is determined by two parameters and the rernaining two are determinable, even othenrise as
seen before.

Also from the above stated relationships for dU, dH, dA and dG it can be derived directly for fixed chemical composition the folloling relationships:

r- (#)"=(#),
(#),

(4.44
(4.48)

p=-(#).= - (#),
V=
and

(#),
/!G\ - |.rtJ'
65

(4.4e) (4.so)

s-- (,+)"

4.g

GIBB'S HELMHOL]Z EOUATION

It is known that putting values of S as in Eq'(4'16)

G=H-TS

G=H.t(**),

dividinsbyl

or
or

+-+ (#)r= + +[+ (#), I=+ or ## =-+ [%(9o1,

[a

(^qp]
JP

La(yn

aH

(4.51)

SimilarlY it can be derived that

[a (^ArDl La(1^) I

- ^u

(4.52)

TheEqs.(4'51)and(4.52)areknownasGibb,sHelmholtzEquationslorfreeenergiesas
they vary with temPeratures'

4.4

FUGACITY
system doing only mechanicalwork It has ben shown earlier that for a

66=VdP-SdT
and at constant temperature when

dT =

dG = vdP
For one mole ol an idealgas

therefore

(4'53) component across can be in equilibrium with only one It can be imagined that a gas mixture this system to that component only' Hence in a diaphramwhich is permlable (mixture side) dG (pure component side) = dGi pressure of that component on the mixture p"tti"r 'p tn" i" *n"'" or therfore dG = RT side. r LL^ ^. pressures as limits of G and the corresponding This can be integrated'over known (4'54) Gz Gt = RT ln (Pz Pr will be one atmosphere taken as agreed standard in which and if conditions for G are to be (4'55)

V = RT/p

dG=nf'Oplp=RT'dlnP'
;';p

'

/Pr)

then

will take the form as For an ideal mixture of gases this

G2 = Go

RT

ln Pz

Gi = GP + RT ln

Pi

(4'56)

66

it can also be imagined that an ideal gas mixture can be in partial equilibrium with only one component across a diaphram which is permeable to that component only. Hence in this
system
or

therefore

dGi = RT ]n pi

dG bue comporcntside)

where
RT ln

= dG (mirctrre

pi

side)

g.5n

is the total pressure on pure side or p on the (4.58)

mixture side. On integration it again leads to

G = GP +

pi

Strictly speaking this equation is applicable to ideal gases or their mixtures only. The free energy-pressure relationship is linear in that case. But for the real gases as pressure rises the integration of this equation does not remain linear and poses sonre difficulties. lewls, the larnous thernrcdynamics scientist introduced a new term called 'fugaclty'and mathematically

dG; = RTdlnt RT d ln f = G + I where On integration

defined it as

(4.5e)

is the integration constant and it is so

tS f=p chosen that P+0 Mathematically the functions U, A and H can also be correlated in a similar way as:

as in Eq. (4.6) Since 611 = TdS + VdP entropy = VdP V = RT/P = RT d lnP = RT d ln f dA = - SdT - PdV as in Eq.(a.10) As at constant temperature = - PdV = - RT(dVM = RTd lnV dlnV n=l"t therefore JVi as in Eq.(3.13) dU = TdS - VdP As under constant entropy = - VdP or at constant and since

(4.60)

(4.61)

The introduction of such a function ensures linear relationship between allthese extensive properties, U, H, A and G and logarithm of fugacity in any state of any gas.
For an ideal gas, fugaclty is equal to pressure at all prassures. Similarly for gas mixture

= - RT(dP/P) = = - RTd lnf

RTdlnP
(4.62)

the fugacity of each component equals partial pressure, as the total or also partial pressure tends to be zero. The fugacity of a component in an ideal gas mixture is numerically equal to the partial pressure of that component. For an ideal or real gas component the pressure is mean of the fugacity and the
pressure it wouldhave if it had behaved as an ideal gas. f=P then P+0 Therefore flP=1 P+0then and lf a gas mixture is separated by a diaphram trom one of the constituent gas on the other side and depending upon the fugacity values ol that component on either side of the diaphram the diffusion of that component acrqss the diaphram willbccur if

RTd lnP(pure) r RTd RT d ln f (pure) * RT d

lnPi
ln ft

(4.ffi)

(4.e)

67

as is obvious like mechanical equilibrium and in the direction from higher to loiver fugacity side !n terms of Pressures of the component in a system' Therefore fugacir.y represents the escaping tendency above relationships using equation of state and

Fugacity values can be calculated frcm

compressibilitydataanditsvariationwithtemperatureandpressure' Fugacityisalsoapotentialtermlikeanyothertermdefinedearlierindicatingnatural process, unnatural process and equilibrium state' very lor and hence can be solids and liquids do have vapour pressures which are with solid/liquid as the case may be equated to as the fugacities in gas phase in equilibrium fugacities' by equilibrium considerations solids and liquids do have
and hence

4.5 ACTlVlw
with the surroundings' The Activity of a component is defined as its ability to interact This ability is maximum when fugacity is activities of pure substances is therefore maximum' of fugacity of the substance in The activity has therefore been defined as the ratio maximum.

thestateinwhichitexiststothefugacityinitsstandardstateas

t t=F

Of

-fi af,=

(4.65)

f,

atmospheric pressure at the temperature under tempertaure under consideration or gas at one or gas phase' is stable at the given consideration. Obviously only one, solid or liquid The fugacity in the standard state is temperature, excepting the transition temperature. activity is unity for pure substances' Since nornrally described uyin" symbol f and ltence take pure substances alone as standard states' standard state is arbitr4ry it is not necessary to

and the i th component' The where f and fl are the fugacities of pure component at one atmosphere pressure and at the standard state is commonly pure liquid or solid

ltiscommonpracticetotakelwt%dilsolutionasstandardstatedealingwithmetallicsolutions With the abow ar= (t I GP) a = (flP) or

andhence f =f'a
and since

or

= aGP
(4.66)

and to are fxed and constant, lherefop

and or

RTdlnf = RTdlna = dq RTdlnt = RTdlna = dGi

{4.6n

The similarity in activity and fugacity is obvious' l lntegrating from the standard state GP to anY arbitrary state

at

1 at f = f
(4.68) (4.6e) (4.70)

!=

and
and

RT lna = G RT lna = Gi -

Go
GP

and on differentiatino

is almost proportional to fugacity and the This activity is also a potentialterm since it be a potentialterm' lt indicates that if activities latter being potentialterm so activity also should 68

,,- Art.- ..o\ RTdlns=d(G-Go) RT d ln a;= d(Gi - G1

$'711

on either side of an interface of two phases in a system are the sar, then the system shall be in equilibrium. lf the two are not same on either side of the interface then the component with higher acJivtty shall'hare a tehdency to migrate to the region of lower activity zone across the boundary, if physically otherwise possible.

4.6

CONCLUSTONS

The parameters like intemal energy, enthalpy,work function and Gibb's free energy have been the potential terms under their characteristic conditions. These energy properties are extensive properties. Potentials are intensive properties and the difierentiation of these two must be properly understood. The properties like temperature, pressure and chemical potential are intensiw properties and are potential terns of one kind or the other and which make the heat flow (underthermal potential gradient), make work exchange possible (under pressure gradient) and make chemicalspecias mow (under chemical potential gradient). The values of the potential terns decide whether the system is at equilibrium or is poised for a spontaneous change or whether energy will have to be supplied to make the system move in the desired direction.
The terms fugacity and activity are directly related to each other. lf say two immiscible

liquids like a slag and a metal or like oil and water are in equilibrium with respect to certain componentthe activity of that component in both the phases must be the same. ln otherwords the fugacities also must be the same and since and which in turn means that their chemical potentials in the two phases must also be the same. Therefore the terms fugacity, activity,
partial energy properties under the characteristic conditions and finally the chemical potential means the same potential term, only in different forms, that dictate chernical equilibria in thermodynamic systems.

69

CHAPTER

HERMODYNAMICS

estimation of entropy5.1
ZERO ENERGY LEVEL

energy and enthalpy of a The first law allows measurnent of changes in intemal not in absolute terms but only system when therrnodynamic processes occur, though energy or enthalpy are purely arbitrary' Both relatively and hence the zero lewls for internal

oftheseareenergyparameters.Theentropydefinedbythesecondlawisa]soaenergy in a thermodyp.r.*". fne seJonO law allows measurement of only entropy changes from the second is not determinable namic process but the entropy value in absolute terns
law.

The Carnot cycle leads to a relationship

_tz

and Tz are fixed when q and which states that the difference in temperaturqs Tl respectively' The range of q2 amounts of heats are then exchanged with the surroundings the nature of the system in the carnot temperature scale orrer Tr and T2 is independentof by adiusting the realvalues of cycle. ltcan rswett iefixed as on Oo to 1000 Celciusscale lower and higher ranges of the same qr and qz . TIre same scale could then be extended to Cas zero degrees abso.lute. or 0o K' As Celcius scale. From this it comes out to be '27go energy and entropyreduce both energy andentropy decrease with fallingtemperaturewill to zero at absolute zero temperature ?

ftt =

gz lqt

fact that though internal energy which is just not the case. This is also obvious from the to zero at absolute zero temperature' changes with temperature it can not be extrapolated experimentally fromJCe OT orJCv dT Energies at higher temperatures can be estimated these have not been and these can be extrapolated. to absolute zero temperature' But energy to even internal obsenedtobezero at0oK. Thus anyassignment olzerovalueof

because then the heat

Allpuresubstancescannotbeassignedazeroenergyvalueatabsolutezero and of formation of compounds will have to be zero at absolute zero

elenents at absolute zero temperature is purely arbitrary.

The integration of Gibbs-Helmholtz equations AUfl" dT d (AAfD = dT d(AG/T) =

and

^Hff

gives

separately +

and

S T

=-f;, Sor*ru =-f'" Jrr 4or*r, f

(5.1) (5.2)

where Iv and Ip are integration constants indicating the constant volume or the constant pressure conditions of the systens. These constants Iv and Ip n not be determined from first or the second laws of thermodYiramics and empirical methods alone becorne necessary for their evaluations.

5.2

ZERO ENTROPY LEVEL

The entropy variation with temperature has already been shorrln earlier
the specific heats as

in

terns of

dSy
and

= =

Cv
Cp

dT

T
dT

dSp

and on integration leads to

Srv
Srp

Q = eOV

-d

Sop

-{

"uS

(s.3)

where Sgy and 36" are integration constants or values of entropy at absolute zero law temperature under constant volume and pressure conditions respec'tively. Again second by itsetf can not solve this for evaluation of Sq, and 36"values except by direct experimental
work.

"rS

(5.4)

Nernstwho after analysing the data of variation of AG and AH with temperature' par$cularly at lower temperature region, found that aG/T and aH/T tends to zero as the temperature approaches zero value as schematically shown in Fig 5.1.
tt was

Fig. 5.1 - Showing schematically the observations of Nerns't about variation of Mf and LG of reactions with
o
tG

temperatures.

I
TEMPERATURE

+
71

d (4G) AT

a(AH)
dT-v

^
J+O

T+O
slnce

#=-as,

AS= 0
T+O

(5,5)

.Nernst generalised these findings in the form of a statement that for all reactions ln which substances are ln condensed state AS is zero at the absolute zero temperature. This is known as Nernst's Heat Theorem and is one of the early statements of the third lar of thermodynamics. Hence if reaction occurs as

A+B=

AB

and if the entropies of elements are assigned zero values as per the aborre theorem then the entropy of the compound AB is also zero at the asbsolute zerc temperature. This is in fact what the Nernst Heat Theorem states. The combined statement of the first and the second laws of thermodynamics is

the entropy change of the reaction is given by AS(reaction) = ASAB - ASA - ASe

dG= vdP_sdT
and this can take the form

or
at constant

dAG=AVdP-ASdT

H=
pressure

^v#r

^s
=

(H),

- AS = 0
T+o

(s.6)

6Q=AH-TAS Similady differentiating partially with respect to temperature at constant pressure

("P),=(H),-'(H) -*

(5.7)

putting values of

therefore
Hence

(5.8)

ACp =

o al

T=

unless

t (#F),

is infinite and which is not

at all so. According to Debye's law

henceat T=0

Cp or Cv c T3 or

Cp or

Cp or Cv = kf3 Cv=0

where k is constant

Hence the specific heats are zero at absolute zero temperature and hence the isothermal processes like change in pressure and/or volume, since without any heat exchanges as Cp and Cv are zero, therefore occur without variation in entropies.
72

or

(H),=o
(u#)"=oas r+o
at
absolute zero temperature.

(5.e)

and
5.3

(5.10)

or in other words the entropy attains a value of zero

THIRD I,AW OF THERMODYNAMICS

The third law may now be stated as that the 'entropy of any homogeneous substance which is in complete internalequilibrium may be taken as zero at zero degree absolute temperaturc^ Complete internalequilibriurn means that unique lorest energy state which is obtained in the crystals when cooled under perfect equlibrium
conditions, such that the atoms occupy uniquely ordered arrangement and hence the uniquely lcwest energy state.

first and the second larrus of thermodynamics but for the third lavrr proof can be given in terms of quantum statistics. It should be noted that, similar to internal energy and the enthalpy, the entropy of elements at the uniquely loruast energy level is zero at absolute zero temperature, is again arbitrary. This is however fruitful because this also, as a consequence, leads to that entropy of a compound at absolute zero temperature is also zero, provided that the compound is in complete internalequilibrium.
There
no theoretical proof for the

is

It is rather difficutt to achieve the state of complete internal equilibrium and hence atons in compounds are not that orderly arranged and hence may not have zero but some entropy which might cause error in calculations.

5.4

EVA!-UATION OF ENTROPY AT HIGHER TEPERATURES

The variation

of entropy

of a substance with temperature has been shown in Section

3.5 and 3.6 as at constant at constant

volume Sr2 = Sr', * -f lr

pressure Sr, = 91,

. Cv.

dl nT and,

(5.11) (5.12)

. I';,
cv

Cp . d lnT

lf this integration is carried from 0o to a temperature would reduce to :

K then using third lzur these equations

(5.13) (5.14)

at constant

volume

sT2

= f, ."0

dln T

and constant

pressure S-, =

Cp dln T

lf this is split into two different temperature zones one lover tha4the Debye's characteristic temperature 0o (which is generally around 15o K) and the other abow this
temperature then.

73

ptltting

^9o 65r, = J6 value of Cp = k 1 as per Debye's 1

?o'.{" ?0,
law

(5.15)

then

lsr, = /o

S ot - l]j ?o' kf ot.{" ?o' =t

=

{. td" * d'
Oo K

?o'
(5.16)

as the first term vanishes

at T =

aSlr= Jcrtrol

tt;+ dT

orwherethefirstterm on the right hand side is the heatcapacityatDebye'scharacteristic temperature. This can be solr,ed graphically by plotting either Cp /T vs T or Cp vs. ln T. Theareabetweenthepoints 0oand Tz under the curve bound by thetemperature axis shall bd the value of the second term on the right hand side and when 1/3.Gp16oy is added tn it shall give the entropy change required. This presumes that upto temperature T2
no phase change occurs. lf phase change occurs in between, before Tz then the equation will

have to be extended as in Eq.(3.41).

o ln a generalised form the values of Szga K are known from the values of Cp between the temperature range 0o - 2980 K and are available in tabular form for many substances and hence entropy of a substance at a temperature T may be evaluated as :

"u.S (5.18) s?=s3se.*1t " "rS = s2sao-C*", cpdtnT the superscript indicates standard states.lf there is a phase change in between then the
entropy change will be given by as discussed in Section (3.11). Example : Calculate the standard molar entropy of zinc at 3000 C assuming that it follops Debye's equation below 25o K. Assume average mean specific heat for solid zinc as 0.36 caUg/0o K and that at 25o K is 0.091 cal/0o /gram.

S?= S2sa"+fr J 298"

= Sggeo*dru"

Cv dlnT

(5.17)

sotution: ASsoooc=Asgzs"k =
{

f;'
Cplave)

As+
x

f::'
ln 25]

cp.drnT

Cetzso)

'+

[ln 573

0.03 + 1.931 = 1.961 cal/0o /gram 1.961 x 65.5 = 132 caVOo /g.mole It is generally not so accurate to take mean value of specific heat like this over a temperature range. ln fact Cp value in this temperature range must be evaluated by experiment and then the integral 25-5730 K is evaluated by plotting Cp vs. ln T and the area

74

between the limits 25o and 5730 K shall be taken as precise.

the value

of that integral. This is more

5.5

CONSEOUENCES OF THIRD IAW

The coefficient of thermal expansion and compression tends to be zero as temperature approaches absolute zero. This will be obvious from Ma,xwell's relations. That is

"=VIFj,
substituting Eq.(4.46) in this gives

1 /av\

cr= -(r5)r|=o

asStendstozeroas

T+

(5.1e)

*=1 /.48\ P

"

(ar/v
asstendstozeroas

substituting Eq.(a.a5) in this gives

U=(#)rf =o

J+o

(5.20)

It is also true that the third law itself suggests impossibility of attaining absolute zero temperature. This can be prowd thus :
Let us imagine a Carnot cycle which is operating between 0o and f X. tne entropy during such a cycle is zero and hence the entropy change of the cycle : change

fr***=o
The term go finite quantity and hence the only alternative conclusion possible is that Oo K is not attainable. Therefore it has been stated that 'no definite serie of processes could lead to achieve absolute zero temperature'. The third law therefore finds a way out to estimate absolute values of entropy based on quanturr statistics.

can not

be so because it is a

ff

at zero absolute is zero and hence Qr/Tr must also be zero. But this

to the entropy of uniquely stable arrangement of elements is nothing but convention. The assignment of zero value to the entropy of uniquely stable compounds is a consequence of the above convention and is stated as the
The assignment of a zero value third laru of thermodynamics.

5.6

CONCLUDINGREMARKS:

Third lanl finds a way out to estimate entropy of substances at absolut e zero degree and ihereby completes the nrethod of calculating the entropy of substances. This ultimately is required to work out energy exchanges during thermodynamic processes.

75

CHAPTER

ZEROTH LAW OF THERMODYNAMICS

phase stability

6.1 INTRODUCTION
lf a system is fully isolated by an adiabatic wall and left to itself, it attains a stable state such that no further change is perceptible, no matter how long one waits, then the system is said to be in equilibrium or has attained equilibrium. Left to itself it shall continue to be in the state of equilibrium and shall change from the equilibrium state only if externally acted upon by some constraint. A system may also be in equilibrium with its surroundings in the sarne way. lf a system consists of only one phase, say liquid or solid or gas then left to itself, being

a homogeneous phase it is normally in the state of equilibrium except some exceptional circurnstances. This is what is known as 'stable equilibrium'. This is best illustrated by an
example of a ball resting in a valley. A system in stable equilibrium shall get displaced from its equilibrium state on application of an external constraint, but as soon as the external constraint is removed the system shall gain its original stable state.

lf such displacement, under external constraint makes it stable in some other state then it is said to be in 'metastable equitibrium'. The best example to illustrate this meta-stabili$ is the ball resting in a small depression at the top of a hill. The other befter examples of metastability are the case of a supercooled liquid or a rnixture of hydrogen and oxygen. A human body is most stable in horizontal lying position. Standing vertical, though appears quite stable, yet it is only meta- stability. ln all these cases the system shall move to a stabler form if giwn a chance by initiating the displacement.
On the contrary on displacement, if the system changes to a displaced state, it is said to be in 'neutral equilibrium'. The example for its illustration is a ball resting on a flat plane

surface. ln the chemical and metalurgicalarena quite often it is necessary to know whether a certain phase is stable or not and if it is unstable, what is the stable phase under the given constraints. Similarly it is more often required to deal with two or more phases containing several components in contact with each other. lt is also then necessary to know whether these phases are in stable equilibrium or not and if not, then what is the stable configuration? The former part is dealt with by ascertaining the conditions for phase or phases stability and the later part by knowing generally the chemical equilibria between the phases involved. The cases like two-phase-equilibria in a single component system like liquid-vapour or liquid-solid

can be dealt with in terns of phase stability of an individual phase or phases inwlved in the
system. The thermodynamic studies are confined to stable equilibria only. lt has already been pointed out that the system and its sunoundings can be in a state of mechanical equilibrium, if pressures in both are equal or in thermal equilibrium if both are at the same temperatures. Similarly they can be in a state chemical equilibrium if the chemical potentials are the same in both. The sane holds true within the system itself vis-a-vis the different phases involved or vis-a-vis the different sub- systems within the system itseff under consideration. The concept of mechanical stability is a static one as will be obvious from the example

of overhead tank. On opening the tap at the lower lerrel, water florus down and stays at that lovrrer level, r.e. it has acquired a static stability at the lower lewl.
ln chemistry howeverthe concept of stability is a dynamic one. ln ternr-s of the theory of reaction rates, the system acquires stability only when the rates of forward and that of the

baclcrard reaction exactly match to have no net effect whatsoer,er. The two equal and opposite rates match but do not reduce the system to no activity level. This is why it is a
dynamic concept.

6.2

ZEROTH TAW OF THERMODYNAMICS

This lantr is more basic than even the first lary, although it was discovered only after the first and the second lalvs were formulated and, formalised only after the enunciation of the third larr of thermodynamias. ln stead of giving it the number fourth it has been preferred
to call it zeroth lanrr thereby indicating its more elementary nature than even the first law. This lavv can be appreciated eren without appreciating the idea of temperature derirred from the second lalr. Two basic properties, particularly of fluids and in that also, more easily appreciated in the case of gaseous phase, are 'pressure'and 'volume'. A cylinder and a piston can be imagined to contain a certain amount of gas. The volume and pressure of this gas can be adjusted by the movements of the piston. Let the values of pressure and volume for a certain gas in this rylinder be Pr and Vr . The gas is thus defined in terms of pr and Vr . lf another gas at volurne V2 is brought in contact With this gas through a diathernral wall the two can be brought to equilibrium by adjusting the pressure of the second gas P2. The two gas systens may have the same hotness or coldness or fixed so by placing them in a certain oven or a refrigerator. Out of ihe four variables three may be taken arbitrarily but the fourth will have to be fixed, in relation to these three for equilibrium to reach. lt means that if gas one at pr Vr is placed in a orren and gas two of Vz is brought in contact in the same oven with diathermal

walls between the two , the Pz will have to be adjusted to bring the two gas systems in
equilibrium.

Let us inngine a third gas which is brought in equilibrium with the first one in place of the second with Ps and Vs values such that Pr Vr and Pe Vs are now in equilibrium in the
oven or the refrigerator. Now from the pair 'one-three' the first system is removed and the second is brought in, then the pair'two-three' must also be in equilibrium, as is obMous and obsened in practice. The same need not be true with only gases but shall be true with any other bodies.

This observation is stated in the form of 'zeroth law of thermodynamics, as : 'lf of three bodies say A, B and C, B and C aro separately in equilibrium with A then, B and C are also in equilibrium with one another'. The converse is also true in that if three bodies are in contact, each to each and are all in equilibrium together, then any two taken separately are also in equilibrium with one

another.

empirical parameter hotness or coldness of the system and is denoted by the palmeter T in the form of an equation as

This leads to the fact that the function of P and V for a certain amount

of

gas is the

F (P,V) = T
This then would be the equation of state of that fluid. lt is this function of the fluids, which is nothing but temperature, which has the property of taking the same value for fluids in equilibrium with one-another. The fluid is thus uniquely defined by any two of the three variables P, V and T.

The original zeroth law statement therefore reads that of three bodies A,B and C, if A-B and A-C are in thermal equilibrium meaning thereby that at the same temperature,
Conversely this is possible for fluids only if their temperatures are equal, that is the product PV for each one of the three fluids A, B and C are equal.
B- C are also in thermal equilibrium, meaning thereby that, they are at the sarne temperature.

then

Similarly if Vr
then Vz

Tr

which shallbe the case of mechanicalequilibrium.

of A are in equilibrium separately with Vz Tr of B and Vs Tr of C of B is in equilibrium with Vg Tt of C as they mean same pressure for A, B and C;

Tr

Equally true will be the case of chemical potentials. lf chemical potentials of A and B are equal and that of Aand C are also equalthen they are in equilibrium and hence B and C also shall be in equlibrium from the chemical point of view. Since thermodynamic equilibrium means equilibriumwith respectto all possible potentials, thermal, mechanical chemical, etc., , the generalised statement as above has been made as the zeroth lar statement for an overall equilibrium.

It may also be stated that if three or more systems are in contact, each with each, and are in equilibrium with respect to any one or more of the thermodynamic potentials, then any two taken together shall also be in equilirbiumwith respect to that potential.

6.3

Phase stability

thermodynamic potentials, of all the possibilities, that phase which has the lowest associated potential shall be the stable one relative to the others, lf the phase has a higher potentiat, it shall change over to the one having lcnrver potential.

will also give rise to the conditions under which two or more phases eists together in equilibrium like at melting and boiling points. From the point of view of consideration of

A substance can exist in either a solid, liquid or a gas form depending upon the conditions of pressure, temperature and volume. The knowledge of conditions under which a phase is stable i'e. in equilibrium is important in systematic thernndynamic
analysis. This

Single component phase is stable in its existing form if and only if the rate of change of entropy with its own mass is negative r.e.

(!e\
\d"/

This is obvious because if this is positive then this will be a natural change possible and hence phase will be unstable. Other conditions are that the specific heat values Cp and Cv must be positiVe and the compressibility p must always be positive r.e.

p>o or _+(r+),,,
Free energy must vary with chemical concentration in a certain direction. lt means activity must vary positively with concentration. lf this variation changes or reverses phase is
unstable.. The problem of phase stability can best be understood from the example of liquification of a gas by compression coupled with lorrrrering of the temperature. The Fig. 6.1 shows the P-V plots for a gas at various temperatures. lt is seen that as the temperature is lowered

I ul c 3 o o LI c a.

Fig,6.1 Pressure-volume relationshipfor air as affected by temperature to show the conditions for ltquification of air.

STAELE
PHAgE

VOLUME
the P-V isotherm
is lcnruere.d in position until a temperature Tc

->

- called critical temperature

is reached, belcnrv which the gas liquifies. lt means the gas stability is lost and liquid is formed for a certain range of P and V values at a temperature lower than the Tc . fre gas is stable in the range A-C and B-F but not in between in the range C-F.

has a + ve value of compressibility upto temperature Tc at which a slight inflextion occurs in the P-V isotherm. Belonv Tc at D and E the slope is zero and the gas becomes unstable. A small range before this stage is the metastable alea

As the gas

is cooled (AV/AP)I

C-D and E-F. ln the range D-E the compressibility is negative and hence unstable for gas phase to exist and hence the change to a more stabler phase that can eist. i.e. liquification takes place. Phase stability will be lost and phase transition shall take place if the free energy variation shows a discontinuity with temperature. ln other words a stable phase region shows continuous variation of free energy with temperature. The first derivative of free energy as derived from the combined statement of the first and the second law as dG = Vdp - SdT and hence

(#),

=-g' (#),='

that is S,V and H vary continuously for is an indication of phase lnstability. Similady the second derivatives pzehf ) and the third (a 2C/at ) atso be varying continuously with temperature for phase stability. Phase stability will be lost if heat input increases the temperature in a two phase stable system like solid-liquid or liquid-gas.

= " lffi] the phase stability. Any discontinuity

and

ln magnetic transformation S,V and H vs.T are continuous curves but the second
derivatives of free energy vs.temperature is a discontinuous one. Order-disorder transformation shall be possible if S,V and H show discontinuity in their variation with temperature. These changes do cause abrupt change in sp.heat, coefficient of thermal expansion and compressibility. These are second order manifestations of free energy variation with temperature.

6.4

TWO PHASE STABILITY/ EQUILIBRIA

It is a common knowledge that at the melting point both solid and liquid and at the boiling point both the liquid and the gas co-exist. This is because the two phases solid and

liquid in one case and the liquid and the gas in the other case are in thermal equilibrium. This is because the two phases in contact have the same thermodynamic potential at such critical temperatures. The change in free energy when one component gets transferred from one to the other phase is zero at such critical temperatures.

= AH - TAS, at equilibrium AH = - TAS. The latent heat is enthalpy at constant pressure and temperature and the internal energy at constant temperature and volume. The heat input is latent heat and matches - TAS and hence AG = 0. The lntegral
/eOV should be zero for such changes. ln Fig.6.1 the two thatched areas are equal and
opposite and hence the total effeCiveJPdV is zero when both liquid and gas coexist together. It can be mathematically proved that for two phases to be in equilibrium like liquid and solid, in any system, the temperature, the pressure and the free energy of both the phases will hare to be in equilibrium and this will be possible ff and only if the chemical potentials of all the components i.e. partial molal free energy values of all the components, though different values for different components, are equal for each component in both the phases.

Since AG

-/

9t4.1

Phase Rule
A phase is a homogeneous part of the system u",ith definite boundarie and interfaces or sub- systems. The number of components in a system is the srnallest

with other phases

number of substances in terns of which the composition of each phase in a system can be defined. The degrees of freedon are nothing but number of independent intensive variables to be controlled externally for describing the system completely like pressure, volurne and temperature. The phase rule states that for any system

or

F=C-P+2 F+P=C+2

(6.1)
{6.21

where F is the degrees of freedom, C the number of components involr,ed and P the nunrber of phases present. For systems nornnlly encountered in the metallurgical area the pressure is often equalto atmospheric pressure and hence is fixed at one atnnsphere and the systerns are condensed phases and therefore the phase rule takes the form as

F=C-P+l

(6.9)

because one degree of fieedom in the form of pressure

is

not arailable.

6.4.2

P-G-T Relationships vs Phase Stabitity

On the whole in a closed one-component system at a certain temperature T and pressure R the equilibriurn phase or phases in the system shall be that or those having
minimum value of free energy. The equilibrium thus can be evaluated by knowing the variation of G at constant T and P. But if any of these two also vary then through the relationship of

G-PatconstantforG-TatconstantPorasG-P-Trelationships,asallthethreevary,
may be useful. Phase stabilities can also be appreciated from P-T diagrams but G-R G-Tand G-P-T diagrarns are more appropriate.

The P-V relationship for a single component system as shown in Fig.6 2. lt is clear that at one atmosphere pressure upto melting point Tu solid is stable, above boiling point Te

I
I
I

il

I I I
I

ut9

I
I I ,

EA TEMPERATURE E
F ig.
6

Blx
T

TEMPE

- Pressure-temperature relat

Fig.63 - The free energt-temperature relationship to show relative

iols hips to indicate stabiJity regbns

of soltd, Iiquin and vapour phase in
a single by

stabilitics of phases (shown by

comprent system (shown

solid lirrcs) and their rnetastable

regions (shown by dotted line$.

soM lines) along-wilh rtte trvtastability regiotts (sho*n hy dotted litn).

81

gaseous phase is stable and in bef,ween Tu and Ta liquid is stable. At T both solid and liqukl and at Ta both liquid and gas phases co-exist. As pressure is lowered the boiling point decreases rapidly and the nntting point also decreases but rather slorrly. Consequentty at a certain ternper&r;s Ts all solid, liquid and gas phases co-exist. The pressure at which this happens is much behw one atnnsphere. At temperatures belovrr Ts therefore solid and gas can co-exist together and hence sublirnation is possible but above Ts solid will hbre to change to liquid and then to gas on increasing the temperature.

The sarne conclusion can be drawn from the G-T relationship for sold-liquid-gas phases br a single cornponent system. The fiee energy values are calculated for all phases as they vary with ternperatures and at different pressures. The minimum value of G indicates the stability of that phase under the conditions under consideration. This is strown in F19.6.3. It clearly shorrrs that at lov pressures vapour is more stable than liquid and hence direct
sublimation rather than melting takes place. At high pressures the temperature rise shall result in solid melting to liquid and then converting into vapour. The situation is clarified further by plotting G-T diagram as shorn in F1g.6.4. Below melting point Tu stable phase is solid and abore it liquid. The unstable phases are shown by dotted lines. Similarly if the AG of solid to liquid phase change is plotted againsttenperature the situation is shorrn in Fi9.6.5. lt clearly indicates that AG is negative for this only above Tu temperature indicating its possibility and bdor Tu it is positive and hence not possible.

--_J1og,a
c.
rg

z
arl

d
TI

d
IL

ul

itr, orN*.,
TEMPER,ATURE

TE'{PERATURE;+

Fig.6.4 - Free energt temPrature relatiarahip to indicate Phase snbility itf solid and liquid phases.

Fig.65 - Tlrc free energl

change occurs.

ehange as a
f t

furrction of temperature when plwse

6.5

CONCLUDING REMARKS

Although obviouS stillthe equilibrium between various systems or subsystens within of phases a system has been established by the zeroth law of therrnodynarnics. The stabilitis

".nu"evaluatedknowingtheirP-T,G-T,G-PorG-P-Trelationship'Thisisuseful problens from the point of view of their uses in practice. A phase which is not stable can pose il it is to be used in practice over a certain duration.

CHAPTER

CHEMICAL EQUILIBRIA

equilibrium constant
7.1
INTRODUCTION

is changed further several tinre to obtain the desired chen{stry of the products. Literally therefore there are innurnerable chemical reactions that are canied out in actual practice, particularly in the field of metallurgical and chenrical engineedng. Although these chemical processes are carried out in such a way that the reaction proceeds in fqward direction but the knowledge of equilibrium conditions of such chemical processes is a must to work out the olthernndynanjc study to firs* establish the equilibrium conditims of chemical processes ol interest. lt is from this pc$nt of view tnt this topic has been dealt with independenily in this
chapter. conditions for rnaking the reactions go in the desired direction. lt is tfrus the prinrary objective

Jhe modern day civilization can sustain itsetf by conrerting the naturally occurring rnaterials into a series of products with different chemistry. Eren the already changed chemistry

7.2

THERI'ODYi'IAMIC EOUIUBRIUM CONSTANT

as

Let us consider a general chemical reaction at constant prqs$rre and tenperature

aA+bB+.......

= (cGc + dGo + ....) - (aGn + bGa + ....) where indMdual free energies are described in terns of the respective G values.

where capital letters are used to denote the reactants or products and the srnall letters are used to describe molecutes inrolved in the balanced form of the reaction. The free energy change may be wdfien as AG = 2G (products) - )G (reactants)
(7.21

=cC+dD+......

(7.11

lf the

reactants and the products are assurned to exist in their standard states, then the free energy change rnay bewdtten with suffixe of standard state on each fiee energy value as o AG = (cGE + dGB + ......) (aGl + bGB + (7.s) Subtracting Eq.(7.3) from(7.2), standard and non-standard state equations of free enerry changes and, rearranging the terns suitably, leads to AG AGo = [c(Gc cB) + d(Go Gb + .,..1 ta(Gn -Gl )

"..)

Substituting

s
-

+ b(Gs _ cg)

AG

derived earlier G Go = RT In a in the above gives AGo = [c RTln ac + d RT ln ao + ....] - [a RT ln a,q +

........1

(t.41

+ b RT ln ae
on rearranging becomes

.,....1

(7.5)

aG-^co=Rrrn

4 "l aA'a8. ...

K

(7.6)

in thermodylf the reaction (7.1) is at equilibrium r.e. if the reactants and the products are value constant of is which parameter, the case that in and namic equilibrium with each other is denoted as :

. -..- "S. ln .8. :- .''=

al.aB....

F,N

of the reaction' The term K by definition is called the thermodynamic equilibrium constant of K remains The activities of individual reactants and products may change but the value constant at a fixed temperature for a giwn reaction' (7'8) AGo RT ln K

AG = 0 and and if the reaction is at equilibrium then the free energy change is zero i'e' (7'9) tn"r"tor" AGo = - RT ln K Putting value of R as 1.987 cal/deg/mole and changing to common logarithm
(7'10) AGo = - 4.575 T log K a also is K and hence temperature It is thus clear that the free energy is a tunction of the in eraaluating function of temperature. This is one of the most commonly used relationship would occur in chemical equilibria. This evaluation indicates whether a particular reaction or the other practice r.e. whether there exists a tendency in the system to move in one : as follcnrs illustrations by two explained direction or is at equilibrium. This is best 16000 C at operating a furnace in Example 7.1 : Will magnesia crucible stay in snape the reaction under a vacuum of 10a atmosphere ? Given is the free energy for 2{Mg} + {oz} = 2< MgO>

Hence

AG

is

AGo=-358700+102.6Tca1/g'mole
The value of AG at 1600 + 273 = 1873 K is given as AGrezso = - 166500 cal/g mole

Solution :

stnce

r = Pfig ^&g-. Po,

AGrezso =

RT ln K

= - 4.575x 1873,on

P[ts' Poz ={_

putting aMso =

166500 = + 7600lo9 p2Ms po. or log p2rug Poa = - 21'91 existing are magneln the ambient atnnsphere under vacuum of lStatmos.the components vacuum pressure' The sium vapour and oxygen gas. Each at best can be equal to the is not known and there proportion of magnesium uupou;. and oxygen in the gas phase

1 for solid MgO,the abore reduces to

moles is no alternative but to assurne that these are in proportion to 1 po. = 2 dissociation aftersubstitutingthisinthe above givespo2 + 2pr'rs = vacuumpressure'Butif oxygen only hence gas phase and does not occur then no magnesium will be there in the ptrg and hence

21'90 or ps2 =lO'"'Under the equilibrium partial this situation sincethe ambient partialpressure of oxygen is morethan

that dissociation doas partial pressure shall be equalto the vacuum pressure' First assuming

notoccurthen- 166500 = + 7600logpo,

or

logPoz =

84

and

Given 4cu + oz = pcuzo aGo = - 7g7oa+39.3T cailgmore and 2Hz + Oz = ZHzO AGo = - 118000 + 26.T5T _do_ Solution : Forareaction 4Cu + 2HzO = ZCuzO + ZHz Hess's law gives AGo = - 39300 + 12.SS Tcal/g.nnle orfor 2Cu + HzO = CuzO + Hz AGo - _ 1gl50 + 6.27 T
AG?ozso

pressure of oxygen the reaction shall har,e a tendency to morre tornrards formation of MgO, that is magnesia shall stay in shape. lf now dissociation is considered to occur then product Por shall be equalto 1/3 of the vacuurn pressure which will still be less than when the dissociation does not occur and hence chances of dissociation of MgO are quite rennte. ln other words Mgo has equilibrium oxygen potential equal to rnuch less than the vacuum pressure at 16000 C and therefsre MgO will not dissociate under the conditions of vacuum and is thus stable under the given conditions, r.e. Mgo shall stay in shape. Example 7 '2 : Will it be possible to anneal copper ingot at B00o b before rolling under a gas mifiure of Hz lHz O equalto 102.

The equilibrium constant of this reaction is

=-

1242J caVg mole

* -

acuzo'

PH3

a6u'

PHao

and assuming the activities of solid Cu and CuzO and since putting values for B00o C it gives

K = pHzl pH.o AG = - RT ln K =
12423 =
pH2

as unity the value

of K reduces to

4.STSTlogK

or
i.e

4908 log Ps, / p*.o

tog

lpu"o =

pHzl gn

o = 192'se

ffi

= 2,53

This gas mixture is richer in hydrogen than that when the ratio is 102 . Hence the tendency for the reaction of oxidation of copper is to go towards lefi. The atmosphere in the ingot annealing furnace is reducing towards copper and hence it will be possible to anneal .oppu; in the given case without the danger of its oxidation.

7.9

TYPES OF REACTIONS

Chemical reactions occur either in a single phase as homogeneous reactions or between two or more phases as heterogeneous reactions. The homogeneous reactions can best be illustrated as : a) double decomposition of acid and base in an aqueous solution like

HCI+NaOH=NaCl+HzO
or as b) reaction of two gases like 2Hz + 02 = 2HrO The equilibrium constant of reaction (7.12) is

(7.11) (7.121

K=
oxygen the ratio Hz I

pfrro

lp\" .

po,
of such reactions

which is characterised in such a way that for a fixed temperature and partial pressure of

Hz} is fixed. ln other words the equilibrium constant

85

and shall be proportional to sucfr ratios or it will be equalto fixed ratio for a fixed temperature fixed oxygen partial Pressures. phases like: The heterogeneous reactions essentially occur between two

i)

solidsolid

<ZnA>+<c>=Zn+CO
lMnl + <SiO> = [Si] + (MnO] tsl + tMnl + (CaO) = (CaS) + (MnO) <FezOg> + {CO} = <FesO+> + {CQ}

iD solid-liquid iii) liquid-liqukt iv) solid-gas

activities of The evaluation of equilibrium con$ant of such reactions need the phase, each condensed reactants and those of the products. For the cornponents in a phase' the contacting gas cornponent will be in equilibrium with its o\/n vapour pressure in with their fugacities equated be The vapour pressurs shall be extremely lor and hence could so low will be substantially without inrolving any significant enor. These fugacities, being Therefore the ac'tivities of ranges. pressure and constant even owr a significant temperature to their fugacitie in gaseous phase' the component, in the condensed state are taken as equal purposes, considering the and shall be constant and hence are taken as unity for usual

v)

liquidgas

2[9+{Q}=2{co}

activiUes shall be- different from cornponents in pure state. lf these are not in pure state the generally on the larrer side and unity. Sin$larly the actual values of vapour pressures are are taken ln the lorm of hence are equated to their fugacities and therefore the actlvlties

thelr Partial Pressures.

in molten iron interacting lf the component is not in pure form, like the one dissolved of activities is a must with components dissolved in molten slag or gas then the knowledge of K can be obtained from for evaluating the equilibrium cons*ant. Alternatively the ralue can be worked out when others the free energy data or knowing K the actvity of a cornponent are known.
7

J"

K depends on ttre Since the Eq.(7.g) implicitty means that the AGo and therefore the value etablishing for tenperature, its variation with tenperature will have to be evaluated
is knoyvn' of K at a temperature when its ralue at some other temperature

{V

PERATU RE ARIATION OF EOU ILIB RI U M CON STANT WITH TEM

of thernndynamics giws VdP - SdT variation of G with T in the form of an equation as dG = are in their standard . This may be applied to when the reactants and the products both statesforageneralisedreactionasstatedearlierinEq.(7'1)as

The combined form of first and the second

larrus

dG8=VtOp-S8Ur dGB=vBcP-sSor

andsoon
and so

dcl

= VldP - SRdT dGB=VBOP_SBdT

on

(7.13)

.:-^ each nna by rrrr rho r number of atoms or rnolecules inrrulved the corresponding ^^ah one multiplying
85

inthereaction(asdepictedbysmallletters},theorrcrallprocesscanbedescribedas

d(cG8 + dGB

- lcs8 + dsB .... - asl - bsB ....) dr

.....

-aGl-bGB....; = (cVB + dVB + ....-aVl-bW "..) dP

{7.141

volume

assurning one- atnnsphere pressure as_ standard conditions and putting

The three expressions in the brackets mean the overall lree energy change and entropy change in the overall process. Therefore daGo = A\P dP - ASo dT

change,
(7.15)

dP=0
=

AGo=-ASodT

from definitional therefore

form

AGo

AHo

T ASo
AGo

rcoA9-T
d

AHoaHo

(7.16)

Putting this value in the aboie

AGo ,'=-

aco

v.1n

This is one of the lorms of Gibb's-Helmhottz equatlon valid at constant pressure. lt can be
also written as

TdAGo
dividing by

T (the integrating factor daco _ _ AHodT

dT = -.dT - AGo

AHo

being

tff ) gives
(7.18) (7.1e)

dr

T-T2

or

d(AG"4) _ _ =-F --dT-

AHo

or
and since

d(+,g?r
o(trr

AHo

v.2al
=
or

AG =

or
therefore

- RTlnK,tnus $ d(Acfn=-RdlnK
dlnK =-- AHo

RlnK
Rd

n This is known as van't Hoff equation relating variation of K with T. Tlre elfect of T on K depends on the value of AHo lor the reaction. lf the reaction is endothermic (i.e. AHo = + ve) then K increases with increasing tenrperature and if it is exotheinib (i.e. AHo - - ve) then K decreases with increasing ternperature. lntegratio,n rof.this requires knorruledge of variation of H with T and which depends on ACp values of the reaction. lf AHo is independent of temperature then K varies linearty with ,inrerce of tenperature (1fD. With increase in temperature the reaction will mow in such a way as

dr

lnK AHo dT=T2 AHo dlnK

(7.211 (7.221

Rf

d(w

=-

to nulify the external constrhint as per the le-Chatelier's principle. Exanrple 7.3 : The equilibrium constants of the reaction <NiO> + {CO} = <Ni> + {COz} at g00oK is 4.53 x 10-1 andat1100oK is 3.13 x ioo
.

Find the enthalpy change of this reaction. 4.575 AGgooo = Solution : Using Eq

(29

x 900 x 4'53 x

10-1

87

smilarly

= AGrrooo =

1865caVg/mole

1575 =

do

Since G = H-TSthereforeHgooo=-1865 + 900x (-1.45)

- s Hence - s -

- 1.4sca/smte
and hence catcutated

=#

Enthatpy is senerallytaken at any one temperature.

as

;Jr"-i#:l:;0"-rure

7.4

VARIATION OF EOUILIBRIUM CONSTANTWITH PRESSURE

As per Le-Chatelier's principle the reaction inwlving one or more gaseous componentslphases will only be affected by the variation of pressure and the effect will be such that increasing pressure will tend to move the equilibrium in such a way as to nullify the change in pressure as the externalconstraint. Any reaction which results in pressure increase by way of fornration of gaseous component from condensed phases shall tend to move in fonivard direction upon decrease in pressure and any reaction which results in pressure decrease by way of formation of condensed phase from out of one or more gaseous reactants shall tend to more in forward direction upon increasing pressure and vice-a-versa. For both the situations, for example for a reaction of dissociation of calcium carbonate as

CaCOg= CaO+COz

n=- acuo'Pco, dOaCOg

with increasing pressure the forward reaction will not be fawured and hence K shall increase or reverse reaction will be fawured and vice-versa. lf the pressure is decreased by employing vacuum the process of calcination shall take place readily ,that is, at a loruer
temperature as has earlier been shown in Fig. 2.'t. ln general therefore if a reaction

aA+bB=cC+dD
represents the reaction involving gaseous components then

K=p8'p$
pft'
pB

Will be independent of overall pressure if

and lf this is not so

c+d-a-b=0 then Kp = Kx c+d-a-b*0.

pc+ b 'a

-b

in terms of activities as mole fractions. This is of direct importance in reactions involving condensed and gaseous phases

where Kx is

the equilibrium constant expressed

where

The folowing example shall illustrate the use Forareaction 2Hz + Qz = 2Hz O

of this more

vividly.

KP

= ( vl"o)r(ofr..pa) =

tr#
/ Nxro\z
88

Noa.P
1 =lN"',,| N"r'P
1

=ln,rr,l

NHro\2

p",

or

poa

= No, . P =

Also from Eq.

a giwn temperature Kp is therefore known in terns of AG of the reaction. Therefore for a certain partial pressure of oxygen or equilibrium oxidising potentialthe volume ratio of HzlHz O can be obtained Similarly equilibrium CO/CO2 can also be calculated for reaction like 2CO + Oz = ZCAz . fiee energy of the reaction : 7.4 : The Example < CaCOg> = < CaO> + {COz } AG = + 40250 - 34.4f cal/g mole is What is the highest temperature at which this reaction will not occur in open atmosphere. Also find out the temperature if the reaction was carried out under avacuum of 10'5 atmos. Solution : The equilibrium constant of this reaction is
8<CaO> .F.COzr/a<CaCOs> Since both CaO and CaCOs are pure solid phases their activities are taken as unity and hence

At

(7.8) rd = - 6*pon . - expRr

[#)'

*F

or

Kp Poz= (#)'

K=

It means till nearly 90Oo C is reached, the pressure of COz shall not exceed one atmasphere and hence calcination will not take place tillthis temperature (see Section 2.6) in open atmosphere. Under a vacuum of 10-s atmos K will be equal to this pressure and 40250 - 34.4 T = -4.575 Tlog 10-5 hence orthe required temperature shall be 7030 K. The decrease in ambient pressure has reduced the calcination temperature.

K = Pocoa' = 1 atmasphere' Since AG = - RTInK = -4.575 T log K = 0 = 40250 34.4T=40250 or T=1170oK=897oC. or

34.47

7.5

FREE ENERGY. TEMPERATURE RETATIONSHTPS

It has been shown that G = H - TS and H and S both change with temperature as shown in Section (2.11.2iland (3.6) Therefore G also must vary with temperature. Since both H and S are not measured in absolute terms but only relatirely with some reference
state, G also is measurable only in terms of reference state or, only changes are measurable' Hence AG = AH - T AS and if all the reactants and products are in their standard states

then AGo=aHo-Taso for a process AFlo = X Ho (products) - : Ho (reactants) ASo = X So (proaucs) - E So (reactants) and
therefore

AGo

The way in which enthalpy and entropy can

(2.11)

be evaluated has been andsection,r,r,i;l"l%""i:'_"1:T"j:", A + B = AB

= [X Ho (products) - : Ho (reactants)] - T I: So (produas) - : So (reactants)l = AHo (reaction) - TASo (reaction)

dealt with in Section

this can be illustrated by an example: Example 7.5 : Calculate the standard free energy of the reaction [FeSJ + <C aO> = (FeO) + (CaS)
89

from the follo*'ing data

AGol = -307100 - 51.28 T AGo2 = -283100 - 42.93 T AGos = -64080 - 19.04 T ({ 2[Fe] + {Cz} = 2(FeO) AGo4 = -1257N - 30.69 T (5) <CaS> = (CaS) AGos - + 19000 + 9.0 T Solution : The required reaction can be worked out using Hess's lav by algebric summation of the given reactions and in turn it also gives the fiee energy change of the reaction by the conesponding summation of the fiee energy values given as: Add (-reaction 3) + (-+eaction 1) + 2 (reaction 5) + (reaction 2) + (reaction 4)
to give the required reaction. (the - ve sign of reaction means the reaction in reverse) The free energy change is thus : = -AGos - AGor + 2AGos + AGoe + AGoe

(1) 2(Ca) + {Oz} = 2<CaO> (2) {Sz} + 2(Ca) = 2<CaS> (3) {Sz} + 2[Fe] = [FeSl

380

14.7A

cailg.mol.

The enthalpy AHo of chemical reaction

is

substantially a constant value without

variation with temperature. But ASo does change with temperature and also with volurne considerably. lf these are plotted vs. temperature for a reaction the net effect of H and S can be graphically evaluated to work out the variation of G vs. T. The G vs. T relationships are varied depending upon the nature of the phases invofued and volurne changes accompanying the process. These shall be discussed later in Chapter 14. As per third lary, elements do not hare enthalpy or entropy at Oo K and therefore the free energy of compound is taken as free energy of formation of compound from respective elements. lnotherwordsforareaction A + B = AB AGo=GoRa-GoA-GoB

= GoAB since Gol and Gog

are zero.

K) are determined using specific heat data and Kirchofi's Law and are plotted in tabular forns so that AGo for any other reaction at any
ln orderto simplify the matter Gole (2980

higher temperature can be evaluated as follqrys Forareaction MnO + C = Mn + CO

AdbE = Gtoo.o +

GRtno.o
Gf,tnroo

GF,morruo

GEr*o

=
7.6

Gtoanro

The AGor value at any higher temperature can be evaluated using the enthalpy and entropy data and Kirchofi's Law. CONCLUDING REMARKS

The ewluation of thermodynamic equilibrium constant is a major achievernent in understanding the chemical equilibria since its knowledge gives the equilibrium positim which can be juxtaposed with the real life situation of the reaction to work out, if any, the desired direction in which the reaction has to be rnade to more. lt also gives the parameters which could be used to make the reac{ion mow in the desired direction. lt also gives the limitations of making a reaction move in the desired direction as reaction can rrpve only upto equilibrium, and that too, often not even upto the equilibrium state but nu.rch ahead of it.

90

CHAPTER

PHASE EQUILIBRIA
SI NG

INII

LE COM PON ENT SYSTE[V

r"

clausius-clapeyron eqnatior
8.1
TNTRODUCTTON

ln practice metals are often heated to high temperatures for their processing in either solid or liquid state. As temperature rises the vapour pressure of metals in gas phase increases and may become substantial. The equilibrium vapour pressures of metals are of direct interest. Firstly if metals are to be kept at high temperatures for a prolonged period il: can lead to a substantial metal loss via vapour forrnation. For example in LD steelmakinll process almost one percent iron is lost in vapour form which not only is a net lqss but poseri pollution hazards. lf such losses are to be minimised then conditions will have to be generata to make vaporisation rninimum. This requires the knowledge of equilibrium vapour presiurr of metals or broadly, the thernpdynamics of single component multi-phase system is requiret o\r a temperature and prasbure ranges of interest. Similarly for dealing with alloys tht, thermodynamics of mufti-component, multi phase system o\,er a temperature and pressu' ranges shall be of interst.
i
r

The melting point and boiling point by implication means those temperatures wher transitions solid-liquid and liquid-gas occur when the ambient pressure is one atrpsphere When pressure is difierent, the m.p. or b. p. do change. The equilibrium solid-liquid, liquid-gat
or solid-gas, as a function of temperature and pressure therefore needs to be established. The equilibrium phase i.e. stable phase under a girren set of conditions can be ascertained fronr

the P-T, P-G, G=T or P-G-T diagrans for such pure components as described in the previous chapter. The lines separating the two adjoining phases in such diagrams are
univariant i.e. with one degree of freedom and needs to be expressed mathematically tc the equilibria involved. These are nothing but the interrelationships of two-phase. single-conponent system with ternperature and pressure .
explain

8"2

EQUILIBRIUM IN SOLID-LIOUID SYSTEM

as

Let us imagine a pure substance system at its melting point T when both solid anc liquid coexists in equilibrium at a pressure P. lt also means that their free energis are equa

Gl=Gs

Let us irnagine that pressure changes by an infinitesirnal ammount dP and as a result the temperature changes by an amount dT to establish a new equilibrium and in that an infinitesimaly small amount of solid or liquid may change orer to the other phase. lf the

associated free energy changes in solid and liquid phases are dGs and dGr and if the system is isolated then these two free energy changes must match as

dQ =

dGs

(8.1)

The vapour prqssure of both under the given conditions are expected to be very small

and hence their fugacities can be equated with vapour pressures considering the behaviour as like ideal gases. ln that case if dP is the change in the equilibrium vapour pressure of this system the combined statement of the first and the second law can be applied to both solid and liquid phases as : dGl = Vr dP - Sr dT (8,2) dG5 = VsdP
It is also certain therefore that

- S"dT
Ss) dT

(8.3) (8.4)

or

VrdF-SidT=VsdP-SsdT
(Vr

ss\ /Afu_r.)\ /dP\ _ - /sr- v"f _ lot/"' lu,lavr,-"il

At equilibrium AG

- V') dP = (Sr -

(8.5)

thus

_ ^H l *,J., = TAll

/dP\

= 0 and therefore AH = 16 g.

(8.6)

where AH is the latent heat of mefting per g.mole and AV is the difference in molar volumes of liquid and solid phases. This is known as "Clapeyron Equation" interrelating the variations in temperature and pressure for maintaining the equilibriurn between the two
phases. lf AV"
-1

is positive , as is normally the case, and if AH"

is a positive quantity as is

normal,

*" (*+)..

will be a positive quantity i.e. as pressure increases the transition

temperature should also increase.

ln other words the equilibrium melting point shall increase with pressure and vice versa. However for ice-water system AV. - r is negative

and hence

(:+)",

is negative and which is fully exploited for the game of skating on ice

wherein the skate pressure increase shall decrease the m.p. of ice and hence help maintain ice without melting for skating purposes, i.e. skating is readily possible.

8.3

EQUILIBRIA RELATED TO LIOUID.VAPOUR SYSTEM

ln the previous section solid to liquid change was logically analysed to arrire at some

mathematical relations. The same logic can be applied here to analyse the liquid-vapour change. The same thing need not be repeated here but the equations shall differ only with respect to change frorn solid to liquid and from liquid to gas phase as follows: Therefore as in Eqs. (8.2) to (8.4)

(Vv-VtdP=(Sv-StdT dP _ AS(v*tt dT - AV(v- /r

Vr = Vv
92

(8.4

since Vv >> Vr therefore AV = Vv and

(difference of liquid and equivalent vapour volumes)

or

ldrl

as usualy the vapour pressures are very lcrrv, it can be assumed to behar,re ideally then vapour pressure will be = RT/P as per ideal gas equation and hene

/ dP\ \ /eq

AHv
=

TVv

{8.8)

or

y Pv' AI{v where Pv is equilibrium pressure; /!ly) = 'apour Rf lorl"o AHv /dpv\ = A4 . -' or or dlnP = *T' dr l,*,J,, Rr'

(B.e)

'This equation is one of the most famous and useful equations dealing witn vapour pressures of and is known as 'Clausius-Ctapeyron' equation. lf AHv is assumed to be independent temperature then on integration it leads to

ln Pv =

Ary * I where I is the integration constant

RT

(8.10)

positive which correlates the vapour pressure with temperature' Since R,T and AH are all

quantities vapour pressure of any substance increases with temperature and vice versa: 3270 C are Example g,1 : The densities of solid and liquid lead at its normal melting point of caUg at its 1190 is lead of fusion of heat The found to be 11 .05 and 10.645 g/c.c. respectively. the same. remains practically pressures melting point. prove that the m.p. of lead at erren high derivatives to Solution : The basis of solving this is to correlate the volume change on melting of pressure and temPerature' The gram atomic volumes of solid and liquid lead can be calculated as

= 1e'8oecc solidlead = **# = ffi liquid lead is = 19'445 cc and similarly for 1190 * 20_7 ,,, ,,_, _ 6443.5cay0olcc dp = dr=@--va = -2657?atmos/0o changingfromlcal - 41.193ccatmos 1126572 dT/dP = 376 x 10'7 0o /atmos = or
When P = 1 atmos m.P' of lead is 3270 C, when P = 100 thendP = l0OandthereforedT = 3'7

x 10-3 oC
c
is giren by
:

1 00 atmosphere pressure Hence the melting point of lead shall increase because of application remains unchanged' practically it hence and UV onV O.OO37. 6 and which is negligibly small

l*rrnpr" 8.2 :

Vapour pressure oiliquid zinc above its melting point of 42oo

logPzn=ry+

5.5

1400 cailg atom' The heat of fusion of zinc is 1600 cafig atom, for abow the m'p' and lt is m'p' the solid zinc below belcrrry its m.p. Derive a formula for vapour pressure over Solution : For temperature above m'p' 4200 C

dP$ql

= P RTz

oHY

= d rn P(,iq)
= d ln

and for temperature belcnl its m'p'

dP(sol)

AHs

P(sol)

RT2

93

at the m.p. of 420 C both are equal and eliminating the natural logadthm

log pzn (sorirr) =

and putting values as

ffi

,on pzr

{rq}

given

+ 4.9

8.3.1

Vapour Pressure . Temperature

=P Relationshlps

As AH is expressed in terms of ACp values and since Cp is expressed in a generalised form as:

CP =

a + bT + clacaVrnole/Oo
:

the enthalpy of vapodsation is expressed as

AHy=AHo+aT+pf+l]3+
where AHo , cr, p, 1, etc. are all constants for a given substance. This leads to

(8.11)

rnP=

-#*ffmt**t*
- AbgT + C

*f

+G

(8.12)

or in a nnre simplified form

lnP = f

(8.13)

lf log p are plotted vs inverse of tenperature then straight line plots o\ er a certain tenperature range ?s shown in Flg. 8.1 are obsened experimentally. lf such an experimental data are available AHv br substances can be calculated by evaluating the slope of these plots.

8.4

EOUILIBRTA OF SUBLIMAIION

The abore equations can be suitably modified to develop the equation forthe process of sublimation r.e. the solid-vapour equilibda as:

where AHs is the enthalpy change of the sublimation process

l*J..=
py =

dPv\

hrAHs

(8.14)

*rc
(8.15)

or

idlnPv\=-DAHs Rf t-aT-/
tn

At the b.p. or the sublirnation point the value of Pv is one atrnosphere and if AHs value is known then the integration con$ant can be evaluated and it is used for other calculations
thereafter.

- ff

- c

fintegration constant)

(8.16)

8.5

VAN'T HOFF EQUATION AND EQUILIBRA

The equilibria so far studied and the equations dereloped to establish the equilibdum relationships of vapour piessure with temperature can also be derir,ed from well known van't Hoffs equation as follonts : the equilibria under study can be described as : vaPour (gas Phase) liquid

94

A (n

f u

H
3\
ul\ z\ $r\ a\ z.\

\rt

d -25

6 o J

F\ o\ o\ ('\ o\

z\ a t2
l-

I\

t\ B\

\t \o

\o

5 TE MPER.ATU RE
Fig.8.1 - The variatbn of vapour pressure with temperature as lag p vs. 1/7. The near parallel lines and inverse slope are.characteristics of this
diagram.
and the equilibrium constant K = pv/a where E is the activity of the component in liquid phase and since it is pure liquid phase therefore E is taken as unity,and hence K = Pv. Putting this

value in the van't Hoff's equation giws

dlnpl _ _ -

d(n

AHv
R

ssuning

Al-& to be constantwith tenperature then

ln

AHv - - fr7

+I

(integration condanQ as before'

thisis the sanre equatinn as in Eq.(8.10) derived earlier. Similarty the sane equation can also be derived from Mar<well's relations given earlier in
Eq.(4.4i1).

8.6

TROUTON'S RULE

It has been observed from experimental data that the values of AHv varies linearly with boiling points and that the plots obey broadly the retationship

+!Y = 21 cat/mote/oo IB.P.

(8.14

This is shown in Fig. 8.2. This was first noted by Trouton and hence is known as 'Trouton's

.t
o E

STOPF r

2l

CaLlolt. 5,7

3
Y

Fig. 8.2 - VariatiCIn of latent lrcats of vaporisation of substances as a functinn of their normal boiling points to indicate the validity of Trouton's RuIe.

BOILIN6

POINTS

9K

Rule' stating that the entropy of vaporisation of any liquid is approximately equal to

21

cailmole/Oo K. Therefore at the boiling point this is the measure of increase in randomness on

vaporisation and which is approximately the same for many substances including both the
metals and their compounds This is useful because the value of AHv can be evaluated for a substance approximately at the boiling point using this rule. For example at Py = 1, AHv = 21 x Ts.p. and therefore on substituting these values in Eq, (8.1 6) gives the integration constant C = 1 0.57.

Using this value of C now vapour pressure of any liquid can be calculated at any other

temperature. Example 8.3 : The normal boiling point of copper is 28680 K. Galculate the wpour pressure of copper at 1100o K. \{hat are the assumptions made in solving this? Solution : The vapour pressure is one atmosphere at norrnal boiling point Hence

ln 1 =

1.e#*s68

assuming that the obeys Trouton's rule AHv "yri"* The value of integration constant is.thus C = 10.56B The vapour pressuie at 1100o K will be 21 x 2868 log p, = + 10.568 or 1.987 x 1100

21

2968 cal

pv

= 4.6 x 10-7

atniospheres.

8.7

RAMSAY.YOUNG RULE
It has been observed that for two chemically similar liquids like same family of organic

groups or inorganic liquids like oxides, sulphides, etc. there exists an approximate relationship of \rapour pressure and temperature. This can best be illustrated as follows :
96

Let two such similar liquids 1 and 2 have same vapour pressures at temperatures

Tl

and Tz respectivelY and therefore

or

or
similarly if

AHvr' *.iy+C1 fi
and

lnpr = lnpz
AHv(zt =ff+cz

+=tHffi-(cr-c')**
fz

areanother such two temperatures at which the vapour pressures of both

are Pv and hence it reduces to

subtracting one from the other gives

* = #ffi - (cr -c')#*

Ii - (cl-cr) \' i i, AHvtz) ft-fz\
11

and therefore experimentally it has been found that the right hand side is almost zero

n-t'l
Tz-

(8.18)

Tz

or the ratio of

temperature at whieh the chemically similar liquids have the same vapour to as pressure is a constant. This is known as 'Ramsay - Young Rule'. This is also referred ;Duhring,s Rule'. Conversely 'the ratio of boiling points of two ehemically similar liquids should have the same value.

8.8

RTCHARD'S RULE
for various substances It was observed from experimental data that the heat of fusion
:

observed as varied approximately linearly with their melting points. The slope was

{xM = z - 4 caVmole/oo IM.P

(8.1e)

and since entropy This is shown in Fig.8.3. This is equalto entropy change on melting on melting is materials is a measure of randomness of materials, this randomness forvarious almqst the same. This should be obvious'

8.9

EQUILIBRIUM PHASE TRANSFORMATIONS IN SOLID STATE

equilibrium in the gas phase' lf tions. These phases shall have their ovvn vapour pressures in the solid phases are designated by numbers 1 and 2 then : ASlz-r1 Sz / (8.20) = Av(z-1)

gas phases can The equations derived so far for equilibria between solid, liquid and transforrnabe suitably modffied for change in phase in solid state like austenite-martensite

l*,|". Ul*

dP\

51 =

97

AH(r-z) / dP\ = ffffi j". * [

...

where aHlr -zy is the enthalpy of transforrnation and

V1z-r; is the molar volume change accompanied in the change.

+ I
I

!r
:,
!J

gt

opi. afatlcK

M.A

Fig. 8.3 - Vari"arton of latent heats of melting of various substances as a

function of their metting points to show the validity of Richard's Rule.

v2

<l

TEMPERATURS OK +

MELT'T'A

POINT.s

8.10

VARIATION OF VAPOUR PRESSURE WITH TOTAL PRESSURE

Let us irnagine a liquid in equilibrium with its vapour at ambient pressure P at a iemperature T. lf P is one atnbsphere then Pv shall be the true vapour pressure of the liquid at tenperature T. Let us imagine that the system is flooded with an inert gas to increase the total pressure of the gas phase in equilibrium with the liquid. What will be the vapour pressure of the liquid at the same temperature? Will it be less or more? lt is bound to increase with increase in total pressure and decrease if the total prassure decreases, like application of vacuum as per the le Chatelials principle. Let us therefore imagine that the system liquid and vapour are at equilibriurn at temperature T and pres$lre P when p is the true vapour pressure.Let trs also imagine that rpw the total pressure increases by dP and conespondingly the vapour pressure increases
by dpv Using the combined statement of the first and the second larrs the change in the free energy of each of the condensed and the gaseous phases as a result of this infinitesimal change is given by as follors:

forgaspnase

and for condensed phase dcc = Vc dP - Sc dT considering isothermal conditions dQ = Vg ' dPv 'where Pv is vapour pressure dcs = Vc dPr where Pr is the total pressure and ln an isolated system like this therefore the two free energy changes shall be equal and hence it reduces to

dGg = VsdP

SsdT

dFv _ Vc dP1 - Vg Vs

(8.21)

since Vg is quite sanilland.can be assumed to behave ideally,

therefore

= RT/Pv

or putting the value of Vs

gi\,w :#
a ln Pv =

*?
dlnPv

onrearranging

H =Soe, or
otr

=ff

ae,

18.221

or

thus, as the total pressure increases the vapour pressure also increases and what

S o oe,

(8'23)

wc

qualitatively suggested eariier is prowd here. ln the Eq.(8.22) above the A ln Pv is the difference in vapour pressure at any total pressure Pt and that at any other reference state (nornnlly one atnns) on log scale and A Pr is the difference between total presure ard reference state pressure (one atnns)' Example 8.4 : Calculate the vapour pressure of zinc under 10 atmos pressure at 7000 K. The norral b.p. of zinc is 9000 C and density of zinc is 6.5 g/cc. At,wt'o{ zinc is 65. Solution : Assuming Trouton's rule AHs (zinc) = (900 + 2731 x 21 = 24633 caVg'mole

taking

ln

putting the values This is true vapour pressure and hence ln p,,

Molarvolumeof

= 12'4 -x '10-2 atmos' zincis 65/6.5 = 10cc = 1 x 10-2 litres

APt = Pr

P = - AHS/RT +- 10.57 ln P = 12'4 x 10-2 atmos.

(wherc 10.57 is the inbgralion constant)

Pv = 10-- 12'4

1A-2

Putting values in Eq. (8.22)

sives ArnPv=|--fl#)
or
or
8.11
tn

= 0.001616 or 16.16 x 10 Since AlnPv=lnPv-lnP or lnPv=AlnPv+

lnP
1o_2)

pv = f, r t ro-:trf_rll-to-')l zoo
=

l--T082 0.1256

"

+ (re.+ ,._.. x

pV = 1.13 atnros under a total pressure

CONCLUDING REI\'[ARKS

of 10 atnnsphere at 7000 K.

lt is seen that it is easier to develop mathenratical equations to establish the equilibrium relationships of phase equilibria in a single component multi-phase system and from these to

evaluate the vapour pressures of substances as desired. The equilibria in multi-cornponent systens have not been derived to awid elaboration and complexity.

99

CHAPTER

SOLUTIONS - I Gibb's-Duhent equation and activity laws

9.1

INTRODUCllON

Strictly speaking pure element is only a imaginary concept for it does not exist in reality. Even the so-called 'spec pure' (spectrographic standards) elements do contain impurities, may be of the order of parts per million or parts per billion or perhaps parts per

trillion, But the levels of these impurity;contents are such that these can be disregarded for practical utilitarian purposes. However the fact remains that eren the
so-called pure elements are nothingbut'mixtures' and since these are homogeneous single phase materials, are referred to as solutidns. ln practice therefore we deal with solutions alone, whether liquid, solid or gaseous, may be dilute or very very dilute or otherwise.

The simplest possible solution is a gas mixture beause all gases together form a single homogeneous gas phase at all concentrations of the components. Forrnation of liquid solutions from two liquids, or liquid and solid, or gas and liquid and so on are
innumerable. Formation of solid solutions are also not at allexceptionaland many usefulalloys or ceramic materials fall in this category. The composition of a solution is expressed in weight percentages or, atom or mole percentages or, fractions and, partial pressures, particularly for gaseous solutions.

(atom%)i = total number

ni

number of atoms i of atoms in solutions

n1+ n2+

n3...+

ni

The individual number of atoms can be worked out by dividing the weight percentages by their respective atomic weights. Hence (wt %)i/(at.wt)i _ (atom %)i - (,ut"/o)t /(aLwt)1 + (vtt"/o)z/ (at.vfi)z + . .. twtl"lrZ(afwtli The molar percentage can be obtained similarly by taking into account moles in place of atorns and molecular weights in place of atomic weights in the above expression.
A solution may consists of two or more components of which the largest in concentration is referred to as solvent and the smaller ones as solutes. A multicomponent solution can bedescribedas consisting of atoms or molecules of components 1, 2,3,.... i as

(nt + n2 + n3 +

ni

) total atoms or moles. lf the solution contains only two

ternary and so on. The minor uncontrollable components then it is termed binary, if three as a large number of components are there like impurities contained therein are disregarded. lf solution' in iron and steel then it is a multicomponent

AccordingtoDalton.slawofpartialpressuresforagasmixture

of the component in solution and P where pi is the partial pressure and Ni atomic fraction thermodynamic properties of a solution are is the total pressure of the gas mixture. The components because of interaction of the most often quite different from those of their need to be studied precisely' The thermocomponent atoms/molecules and hence lhese in solution is best expressed in tern's of their partial

pi =Ni

(9'1)

dynamic properties of components

taking free energy property forthe purpose properties as explained earlierin section (4.2). By of illustration it has been shown

that

\oniJr,Rn, nr,n.,.. niand the total property G'of the solution can
1

G' = f+)
(G)'rp

be obtained bY summation as
(e.2)

)i

n'

'n,

Ni

.+r-n3...= n2+ n1+

---

ni

thenmolar G=>; Gi .Ni =GtNt+GzNz+""'+GiNi

Similarlytheotherextensivepropertiesofthesolutioncanbeexpressedas: i_ Vi .Ni = Vr Nt + Vz Nz + " " ' ViNl
Molar

i_

(e.3)

volumu

Molar Molar

enthalpy entropy

).' ": )' ": )'

(e.4)
(e,5)

Fi 'Ni = Hr Nr
Si 'Ni = St

Hz

Nz +

""' ""'

Hi Ni

Nt +

Sz

Nz +

Sit{l

(e.6) (e.7)

Ai'Ni = Ar Nr + -fu ltz + ""' AiNl MolarHelmholtz' Lt1 and so on' free enqgv ,/ 3.{ ctaB's DU H EM EQUATIoN pressure and ternperature gets reduced
The differential equation (4'Q-0)' at constant

i_

to

dG'

ffi)ro*".,..

n,'on' +

i (#)r,*"1,n3, ", n
+

"

dnz +
(e.Bi

/aG'\

lffijr*"1,n2,. " ni'dns

=

""

"on'

'r#)rr", ", ". n, '

6r dnt * f,2dnz a f,3dns +

""" * fr; dn'

(e.e)

Similarly the total property of a solution is

101

(9'10) G'=nr6r+nGz+-ngGs+"''+niGi .' + nidGii + (Gr dnr + dG' = tn1ae1 --gOGz + ngdGg or (9'10a) a {2dnz * Q3dns + ""+ Gidni) On combining E3.(9.9) and (9.10a) leads to' .: (9"11) ildGr+nzdGz+nsdGs+""+nid6i =0+ n2 + n3 + ni) i.e. (nl dividing by total numUeiof atoms/molq:in the solution NidGi = r.rr-oe.r 1 [2dGe + NsdG 3 + tni" i" knorrn as Gibb's Duhem equation' 1 and 2 then lf the solution is of only two coFnponents nanrely

il; "-' or

""'+

' ' '+

(9'12)

By the same treatment Gibb's Duhem equation for

Nrdbr+NzdGz - o dG 1 Nr dG.r = -'ru, oG-, = - (1-N1) dG 2 = (1-Nz)

(9'13) (9'14) all other extensive properties can be (e'15) (9'16)

;"H;.:::,:;",n, forentropy forworktunction forvolume forenthalpy

as:
Nl

Nrdul + Nzdlz + Nsdus"" Nidui Nri-qr.f.fzC$z+NedSs....NidSi

lor !:inary can be stated for any evtensive molat and so on. ln fact the Gibbis Duhem equation propefi Z

=0 =0 0 = hit;At*rutdAa+Nsd!3""NidAi * = Ni OV1 +Nz*!z+NsdVe"'"NidVi 0 ildgt*rutOtrz+NedFis....NidFii

=
A

(9'11
(9'18)
(9"19)

dZr + NzdZz

{9.20}

9.3

FROM MOLAR OUANT1T1ES DETERMINATTON OF PARTIAL MOL'AR QUANTITIES OF SOLUTION

Ers

ThemolargeneralextensivepropertyZatatwocomponentsolutionisgiven

z'; it?t * NzZz

{g'21i

differentiation

{s.22\ to added when solution as given in Eq.(9.20) Gibb's Duhem equation for a two component this leads to (e.23)

giws 67 = Nt Z-; + N2 {Zz +

Zl dNr +

Ze

dt'{z

Nol

in a binary

67 =7t dNr + ;2::Si-: solution Nt + ire - i

hence

by Nr /rtNz gives muttiplying both sides ol the equation {9'23}

dNl+dNz = 0

or

dNt=-ditia
(e.24)

7t+NtZz ffi=-N1 from equation (9'21) Nr Zr = Z - NzZz

N1
substituting this value in Eq. (d'2+1

iives
(e.2s)

Nt

ffi

- - z + NzZz + NrZz
= -.

2 + Zz

(Nr

+ Nzi
(e.26)

Putting

--Z+Zz Nr = (1 -Nz) 2r=z+{1 -Nz)

dz
etNe

p.2n

102

and simihr$

dz Zt=Z+(1 -Nr)--_ dNr

(e.28)

For a multi-component system it should be

2.r = z + (1 -

1,-1.,y

/i{;
\dNtl,u,*"...*,

(e.2s)

It only means that if total molar property of a solution, as it varies with composition of one component, is knorun, then the prtial molar prooerty ef other components can be found one by one using the above relationship"

9.3.1 Graphical

property with conposition of a solution is shown in Fig. 9.1. Graphically from such a graph the partial nolar property of a component
1 and 2 can be obtained by drawing a tangent

Method The variation of molar extensiw

on the curve at the

relernant point indicating

Fig 9.i - lhrintbn nf any molm

extensive

properg of a binary solu-

>i 2
lt

Ti

Fi

tian as a function of composition

the composition at which the partial pr;iperty is required. The tangent is shown in Fig.9.1 at point A when the conceniraiio* i: flr . lt strikes the Zaxis at E at 100% Nr and at F at 100%Nz composition.Theint*rcepts at E and F give the_values of the conesponding partial properties. The partialproperties are shou asZr and Zz as DE and HF respectively"
Graphically

-,._"

i J

I i

Zt=DE=DB-BE=q4-gg
BH =.BA

GA = Z as per the graph

and

E;

i1

Nri stope of the graph ar A

, i1 -Nri tr
Naut

Fr=DF,-z-.. ij
2z = HF = I

N1)

*Z
aff;

(e"30) (e.31)

and sirnilarlv

- {t

Nr}

103

Thtrs it pro\s that the tangent.drawn on the curve at the relevant composition point, intercept on the ordinate gives the partial molan quantities.

g1e

Also at

Nr = 1,Nz

Similarlyat
9.32

or it is the sarne point where curve cuts the ordinate i.e.

= 0 and Z =2t

(e.32)

Nz = 1, Nl = 0 and Z =22 at point J Additional Relationships of Partial Properties

at

C.

(e"33)

For a solution of large on differentiation

amount G' = H' -

TS'

(e.34)

1aG'\
|.6,lr.".,".,...

n,

ont

1aH'\ = |.frjrrn2,n3,...

ni

-r
Gr

/39\
ldnt/Tp,nr,nr,..
n,

te.35)

Itmeansthat (Q.86) = Fir It also means that the relationships valid for free energy of a solution is also valict, in the same
fonnat, for iqldividual components irithe form of the relevant partial molar properties. Similarly therefore

- TSr

ln the same way the cornbined staternent of the first and the second laws of therrnodynarnics for the solution can be expressed as

Ht = Ur - PVr Ar = Ur - TSr

(e,34
(e.38)

dG'=V'dP-S'dT
or similarly dE = VidP - SidT and all such relatlonships shall be valid for solution as well

(e.3e) (e.40)

like

f-aG'\

l,F)r,^',,",..

and
Arso

ni

v'

(e.41)

fH \
\

/l'nt,na,.'.nr

=-s'

(e.42t

and
simirarrysince

/aB') - - Vi =-f r aP l\ /l,nl,nz,...ni 1@) =-Si larl/l,nl,na...ni

te.)
(e.44)

ffi],:*

thus

l+ff],--

(e.45)

9.4

IDEAL SOLUTION

9.4.1 Raoult's l-aw

ln the early days the study of solutions was lirnited to the measurements of vapour preessures of solutiens at various concentrations sf the dissolred cornponent in binary

solution systerns. These ryleasurernerits were neadily feasibte by actual experimental vtork. The observations so made were codified byRaoultintheformof astaternent, linnited
't04

to birnry

due to tle suggested solution," in the solute of the fraction addifion of solute is equal to the mole Raoult. lf pr and pz are partial pressures of components 1 and 2 in a binary sclution at a
sokJtians

ody. 'The bwerlng of the vapo{rr Pressune of a solve!*

certain temperature and if

pf and

pE are the

vapour pressures of pure cornponents 1 and 2

then

tr9- p. ".-=NzOf
P? P2

1-1=N. 71

or

A=t-Nz=Nr
P?

(e.46)

and ll:-P'=ry1 or t-!=rur

where

or \=t-Nr=Ne

P.47)

Nr

and

Nz are the mole fractions of the components 1 and 2 respecti'iely and that
trti =

Nr + Na = 1. lnageneralisedwaytherefore

temeprature

Pl - Pf or since pP is fixed at a certaln and pressure pi c, Ni

Ni

or vapour pressure is are low, these can

(9'48) pressures directly proportional to its mole fraction. lf the vapour be approimately equated with respective fugacities and hence (9'49)

This mathernatical statemenrt is known as Raoult's Law and is often stated in the form that .activity of a solute !n a solution is equal to its atom or mole fraction'. This is shown in Fig g.2 by the diagonal line as the Raouft's law line. The activity of a component is equal to itj actual atonn/mole fraction in the ideal solution and hence Raouhian behaviour is considered as an idealsolution behaviour' Those solutions which obey Flaoult's law are therefore known as idealsolutions and thisholdstrueat all temperatunesandpressuresatwhichthesolution is capable ofexisting. The solution tends to behave ideally at loru vapour prqssures because the vapour then tends

+= 1=3i PPf,

to behave as an ideal gas' ln reality howewrthe solutions hardly obey Raoult's law orrerthe entire composition rance.Fiaoult's law is seen toholdtrueonlyif theconcentrationofthesolvent is too large

d
I
F
l--

Fig. 9.2 - The activity-composition

relatbnship to show Raoultian and Henrian behavioux The deviation from ideality is also shown.

()

ATOM FRAGTION 105

o'6

obviarsf frat of the solvent too small. ln other words it holds true in dilute soltdions only. ln rnn{iltrte solutions the behaviour deviates considerably from the ideality in both pcitive and negative direction. ln.the deviated form the activity is either more than (+ ve dvidion) or less than (- ve deviation) the ideal values. The negative deviation is shown in pracfbe by many solutions like Fe-Si, Fe-R Fe-S, Cu-Sn, Al-Zn, etc. The positir,e deviation b strotn by relatively fewer systems and is typicaly illustrated'by the Fe-Cu system. Near ideal behaviour is shown by Fe-Mn, Fe-Ni, Fe-Co, ionic melts contahing gommon ion like Feo-Mno, FeS-Feo, FezSioa -MgSio+ and the like.
and

9.42 Process of Mixlng

and Connponent lnteraction

ln pure state atoms are surrounded on all its sides by like atoms. Thd process of mixing of components changes the atomiclmolecular configuration such that now unlike donrs are available to sugound it and such number of unlike atoms surrounding the dom increases on increasing the concentration of the solute in the solution. This gives rise to short range as well as long range ordering even in liquid solutions in certain preferential way. This short or long range ordering basically arises due to different atomic structures of the component atrnos and it nanifests as interaction of the components in solution, The solution formation is a natural process at least to some extent of concentrations of the conponents. Hgnce the components have natural tendency to form short Qr long range ordering between unlike atoms. Almost the entire volume together of the components is available for component atonrs/molecules to move. ln other words thb entropy of the components on solution formation positivelY increases. Allthis leads to changes in the energies of the constituent particles on forming a solution and hence energies will generally be liberated or absorbed depending upon the above changes with reference to the characieristics of the component atorns inrrclved in forming the solution. These therrnodynamic changes by no means are insignificant and treating the solution simply as a mechanica! mixture of the components can lead to Yery erroneous deductions.

9.4.3 Solution Models

ln a solution the activity of a component should ideally be reduced down to ils own oropcrtion i.e. atonVmole fraction. But the real behaviour is quite different, Solutions exhibit wide ranging variations in the activities of the component which in turn means equally wide ranging thermodynamic properties as has been experimentally observed' There is there-

lore necessity to explain these obsenations in ternrs of some models based

on

irteraction of component atoms/molecules in solution' Three main theories have.been suggested to e:<plain this namely {1} ti:e classical thermodynamic model assuming formation of cne ci rnore c'f complexes, {2} ti;* statistical thermodynamic model assuming free vclume for vi'nration *f each particle lrl a soiution and, corrconent particles in terms of bonCs in :. sliutici:

i3)thequasi-chemicaltheorywlrichtakes!nr';aecc)''|r!rlih*--pref+r'e"'li-'distribrr-;tionerr'

",c,

Various assumptions have been made in developing these models' Atoms are atonrs supposed to have a discrete size, Valency and electronegativity. \Mren two or more in atoms torm a solution, the differences in these three properties between the connponent size factor solution giw 1se to certain effects. The difference in sizes of atoms give rise to effectcoulombic gires to rise effect manifesting as strain energy. The valency difference electronewhich is sornething akin to effect of groups of atons in the periodic table. The

ln gativity difference gives rise to chemical bond forrnation. All these result ln changes energy on solution formation' 9.4.4 Quasi-chemical Explanatlon of Activities of Without going into the intricacies of these theories the qualitative behaviour it Hence solution' solutions can be reaoity understood from the quasi-chemical theory ol quite in terns belorru. The narne itself indicates that it is something like but not
is described

of chemistry and chernical bonds of the components in solution. of ln condensed forrn, liquid or solid, atonrs do link to each other through formation

in working out the chemical bonds. The quasi-chemical approach relies rnore on these bonds approach as the a limiteci is This energy of solution as distinct from their components. atonrs coming together energy of solution shall be in terms of all effects of the two types of over a and not merely in terms of their chemical bondings. The bondings actually extend quasi-chemicaltheory distance i.e. long-range ordering will have to be considered' The qualitatively explain the does not incorporate ihis comptication either. Nevertheless it does behaviour of solution well and therefore needs to be understood' in a class This behaviour can be understood from an illustration. Let us inugine that he can do so room where several students are seated and if any one wants to run arruay on him and stay with the same vigour if the rest of the students do not exert any influence prevent him frorn try to neutral to,rlards him. lf one or more do interact with him and, say, for it is now reduced running away, he nny not be able to run away with his orun vigour tendency" lf the other depending upon the extent of force (bonds) exerted on his escaping to run auray with added activfu students help him to run airuay by way of push he will be able by others on him will be a exerted o'nore than his own. The exact inffuence of the forces on him and on others or conplex one depending upon the forces exerted by individuals

amongst thenselves'

solution since the component atonE aredifferenttheydohave forcesof different electronic structures' attraction or repulsion amongst themselves, because of their

lrr

This is knoryn as interaction amongst themselves'

or unlike atoms. lf the A-A and B-8. This can be summed up as lnteraction in like atoms both components may attraction in like atoms is more than that in unlike atoms then dcminate positivb deviation from ideality. On the contrary if attraction of unlike atons reduces 'the escaping ""nili then both may exhibit negative deviation from ideality. This attraction be reduced to the shall activity tenrJency of the components to the surroundings and the shall be seen in the activity' extent this attraction dominates and hence negatiw deviation
107

lnabinarysolutionsayo!componentsAandBtheinteractionspossibleareA.B,

dominates then
metts.

interaction exists and in consequence intermetallic compounds like Ax Equally true is that if the unlike atom interaction is too feeble and hence

the examples of which are quoted earlier, the behaviour observed shall be practically ideal. such cases are obviously far. on the other extreme if two different atoms are so widely different
that strong

similar as if in their pure form. Strictly speaking such a situation is non existant because no two different atoms are alike. However if they are almost alike,

The srtx$rrr beco{rFs little more conplex if a third elerrerd say c b & b the tlinary solution. The eartier interaction of A-A, ts-B and A-B are now influenced by the interadion A-c, B-c and c-c and whaterer are the net final fnteractive forces, to that erient, the final ideal behaviour shall be affected and accordingly the positive or the negative behaviour shall be observed. The situation becomes far more complex if more than three components are invorved Le. inmurti-componentsystems. The Raoultian behaviour willbe exhibited by'the components if the atons are similar in nature so that the interactions of like and unlike atoms are correspgndingly almost

By tends to form.
like atom attraction

the solution may exihibit

miscibility :-:ap as is seen typically in silicate

9.4.5 ActivityCoefficient
From the foregone it is quite clear that the ac:ivity of a component can be equated to if ideal in its behaviour, but if there is a deviation then what is the actual activity at a given concentration? in idealsolution ai=Ni the non-ideal behaviour is covered mathematically as
its atonVnple fraction

behaviour indicating that activity coefficient y has a fixed value for a given binary solution. This activity coefficient is often reffered to as yf to indicate that it is valid for dilute concentrations of solute only and hence is distinctly different from y for any other higher concentrations. Activity coefficient has a value at unity when ideal behaviour is observed. For negative deMation, fwill be less than unig while for positive deviation, fwirr nefr*at*r tnan
unrty.

multipv,tq?lilL.,XnJLn9" the atom fraction Ni into the rear varue This muttiplying factor is known as 'activity coefficient'. The ", "l?;lil activity coefficient is not a fixed value, it varies with concentration as will be obvious from Fig. g.2. Most often dilute solutions are under consideration and wherein the non-rdeal behaviour conforms to a straight line
where v is the

9.4.6 Henry's

l-aw

The behaviour

of a

solute. crt dilute concentrations was found to obey

,P

traiqNi

E- Ni *

lt sld $e aetivity of a compoll@B1r-: ln dilute solution is proportional to its atom/nrole fractbn as distinct from Raouit's Law. ln reality it has been observed that for dilute solutions, ilhe solute obeys Henry's law whereas the solvent obeys Raoult'larrv (being

and was ndieed and stated and henice is known after its observer as ,Henry,s

l:w,. j?j]

at very high

108

far too apart from each other and hence negligible interaction occurs to afiect Raoultian
activity.

9.4.7 Standard States and their lnterretations

interactive abiiity with respect to sorne standard interactive ability. The interactive ability is maximum when the material is in its purest form. This pure form can be solid, liquid or gaseous form of that substance, as the case may be under given conditions of temperature and pressure' This is purely arbitrary and without any scientific basis, though perfecly alright' The activity of a component in such a pure form is assumed to be unity and the rest are expressed as its fraction when in impure form. The condition of the component in which form the activity is talien as unity is defined as the 'standard state' of that component for the purpose of calculation of its activities when in non-standard condition. From the definition of standard state any other state of conr,enience, other than the pure form can be arbitrarily taken as standard state. The Henry's larry offers two such alternative standard states. One of which is the infinitely dilute atom- fraction standard state- This is so chosen such that the Henrian activity approaches the value of atom fraction at infinite dilution. lf the Henrian activity is depicted by 'h' (as distinct from ,a, used to denote Raoultian activity) then
The Henry's law line as shown in Fig.9.3 is the ideal line for Henry's law and the vaiue of unit activity is shown by yP on the y-axis. Actually the Raoultian activity
By definition of activity itself, it is obvious that it is a numerical fraction to express the

h=

Ni

as Ni ---' 0

(g.S2)

a=yfNi
coefficient, independent of concentration for dilute solutions. On hi cr Ni and hence hi = yP. Ni (e.53) But yfl is the Henry's law coefficient. On assuming the dilute solution standard state for Henry's law hi = Ni as yP = 1
Henrian scale

where

yf is the activity

z U
a

z :< c

Fig.9.3 - Depictianof Henry's law scalevs. Raoult's law scale to dffirentiate them

I I
C

r\i
,.

5 z

r"rt

. r.

too%
L

109

Bd

This 'rs one of the standard states on Henrian scale. lf there is a deviation from this behaviour then mafrenratically it is equated as where is the activit 6; = Nl . coeficbnt on Henrian scale with relerence to infinite dilute solution standard state.

b the Henry's law coefficient. On assuming the dilute solution standard state for hi = Ni as Yl = 1 Flenry's laru

Abo therebre

"hi t =

(e.54)
r.t,

The intenelationship of these two standard states, nanely one as pure substance standard as state and the other as infinitely dilute solution standard state can be assssed
activity of i relative to pure substance standard

state

acini
while dealing with chemical

\lqfl = "f t' =-N'

physico-chemical processes the energy expure f"e. at change in the process would depend upon the initial state of the system, whether free energy unit activity or impur6 i.e. alalower activi$. Therefore it is necessary to know the and it is state change inrolred in transferring one mole of i from one to the other standard
given by

or

AGo - Gl

(pure subsiance standard

stab) GP (AiUC solution standard stab)

of i AGo = RT ln of i (dilute solution standard state) ' factivity lactVity

(pure substance standard stat-e) (9'55)

= RT ln
energy exchanges.

yP

This is still far too complicated

to deal with

in practice for evaluating activitles or

chemical ln a nrulti-cornponent system the Ni can be evaluated only after complete analysis of the solution to its minute details including the small impurity concentrations' law by way of This is rather too difficult. A practical way out is obtainable from Henry's one weight Percent concentration of a component as its another assumption activity on standard state. lf this is assumed then 1wt% concentration will have unit Henrian scale. Strictly speaking it is

of

hi

= .(#j)rm*wr6*o

therefore at lolrler concentrations

as shown in Fig' 9'3' hi = wt96 i of components in The activity values are thus directly the values of chemicalanalyses the required otherthan components dilute ranjes obtained as weight percentages. No other

ones need be analysed in this case unnecessarily' coefficient lf the real behaviour deviates from this ideal Henrian behaviour, activi$ can be introduced as before as

fr; = [wt%

i] x t
(e.s6)
110

*- "

hi

wtToi

The utility of this practical standard state lies in knowing the free energy associated with the production of 1wt% dilute solution from a pure component. lt is obviously related to the nature of the solwnt and will have to be assessed for each solvent separately. For iron solutions it can be shown that the free energy for changing the component from pure state to 1 vi"/" dilute solution in iron, using Mre and Mi as atomic weights of iron and component i, is given by
:

(e.54 the energy exchanges in processes as absolute values are just not measurable. When reactants and products are not in their pure forms any other datum lerel can be arbitrarily taken for the assessment of energy exchanges" So long as all measurements are made withthis new reference state, problens do not arise. But if some rneasurements are made with one standard state and the others with other standard state then they can be transferred from one to the other standard state by knowing the free energy change for transferring frorn one to the other standard state. Example 9.1 : Molten silver was contained in a crucible of Sis Nl under nitrogen and hydrogen gas mixture at 1400 C for the reaction
AGo = 209000 - 96.8 T cailg,rnole At 4foA Nz equllibrir.lm Si content of silver was 0.238 %. Calculate the activity coefficient of Si in Ag-Sialloy at 14000 C Solution : The free energy change of the above reaction is
< Sis

yf + RT ln [Mre /Mil = (4.575 T log 0.5585yP)/Ui The standard state is like a datum level for measuring
aGo = RTln

N+>

and

= 3(Si) +

2{Nz}

AG?loo

=
=

209000

96.8 T

47054 cailglmole
Prua

since

* = dl,', !fr' ?SiaNq

where

= 0.4 and

dSiaNa

= 1 as

solid

therefore K = (wt.% Si; x ySi x O.4 using AG = - RT ln K 47054 = - 4.575 T {log ([wt.%Si] x ysi
putting values in the above gives

0.41]

log ysi =

7.169 or
-shown

ysi = 0.855

9.5

ACTIVITIES IN MULTICOMPONENT SOLU11ONS

of a component is affected by the solution because of their mutual interacpresence of other solute comporpnts in the same tions. These interactions are far too complicated for conect predictions but it is necessary that knowing the activities of a component in some simple systems it should be possible to
It has been earlier that the activity
mathematically predict that in a complex solution.
Let the activity coefficient of solute

B in a

binary solution A-B be given on Henrian

scale as

TB

hg_B
[wto6 B]

111

if a third element C is added to this solution then value of fB is altered to the extent C has interaction with A and B and hence

rr$-e-c- h0-8, fg or
h6-B-c=1wt%81

where i" tn"t parameter or multiplying factor that corrects the binary activity into the ternary one. ln a way it represents the effect of C on B,
where fd - B - c is th" activity coefficient of B in ternary solution. Itmeans hB-t-"- twr%Bl* x fg (e.60) Sincefa ilself mayvarvwithconcentrationitistakenas fB astheactualvalueatthat concentration.

{e.s8)

t f$-B-c

(e.5e)

Itfollowsthat f6-B-c= tB*

fB

That is the binary activity coefficient when multiplied by the factor, which indicates the influence of C on B, the ternary activity coefficient is obtained. Similarly in a quarternary solution when D is added the activity is given as

n$-a-c fB ,, tB [wt% B] provided the influence of D on C in the form of is negligibly true in dilute solutions. ln a generalised form therefore

'

(e.61)

snnllto be neglected. This

is

fe=

fB'f8'fB..

for a multi-component dilute solution

(A-

Taking logarithms in a multi-component soultion

- C-

6
D

(s.62)

.,

. . i ).
(e.63)

togb=logfB+ bgfS+ bgfB......+ togfb

The experimental data on the influence of concentration of third element on the solute i.e. C or D or....i on B in a solvent A, indicate that for dilute solutions the log fb u". wt% of the third element, the infiuence is typically shown as in Fig. 9.r$. When the solution is dilute the relationship is straight line and the.slope is given by

slope of the
This slope as eB

line = qrq wPh i

(9.64)

has been designated as interaction coefficient or parameter and is expressed

log (9.65) of B. Hence

Therefore
where or
(s.66)

fB = ,. wto/o C "8 e$ indicates the interactive effect of c on cbncentration hB = [wt% B] x fs = i* o/o'Bl x- # x fg , fB

tog ha

on log scale

=
=

logfB

bgf8

+ log fB +
.
$n"z"c)
log wt% B

. bg

6 + flog wt"/B]
(e.64

.... ub . (wt%i) +

"B

(wt%B) + eB

+ eB . (wtoloD) +

112

ERRATA

L /L

)v ,+ *

Dorrgb
EN LA

A&aA
R-C'

Eb

t2
o/o
A

5+5
Poel
E

ugrte

nr
i represented by Nos' I to 8'

Irig.g.4.SchematicvarirltioncfactivitycoefficientofsclluteBasi$.luencad
by the presence of third (solute) element

It is therefore possible to experimentally determine actiMty coefficients in temary systens and from them compute using the aboveequation, within reasonable accuracy, the actiMty of any component in a multi-component system. Although this is valid for dilute solutions the resuhs in the case of even non-dilute solutions have not been allthat wrong. Sonretimes

eB is known but not ef .

This can be found out using Wagner,s

(9.68)

approximation for dilute solutions as

eg Me = eB Mc

where M indicates the atonic weights. lf both are known their accuracy can be verified using the aborc equation. Exanrple 9.2 : Calculate the activity of sulphur dissofued in moften iron under the folloring conditions. % elernent in solution interaction parameter

s
si

0.08 0.75

.E = "$" = -

0.03

Mn

0.025

'

Solution : The or,erall activity coefficient

- 0.30 P - 0.35 Cr - 0.67 Ni - 1.s0 c - 2.50

tg

"5

= + 0.065 = + 0.042
o.oo5 0.002

e8' =,e$i = -

= + 0.110 "8 of S in the complex iron nrelt shall be

togfs

= togf8 + togf$n + togi + log * tog, + bgf$i + bg = eE [%s] * "Sn. 1wt%Mn) * . 1wt%Si) * 1wt%p) + "Ei "E. + e8' .ptzocr; + e$i . (wt%Ni) * (wt%c). "g. (-0.03 x 0.08) (-0.025 + x 0.75) + (0.065 x 0.30) + = (0.042 x 0,35) + (- 0.005 x 0.67) + (_ 0.002 x 1.S0) + + (0.11 x 2.50) = - O.OO24 - 0.00018 + 0.0195 + 0.0147 _ 0.0033 _ 0.0030 + =
lg

Therefore

= 0.5 Hence the activity of sulphur dissolved in iron is

fs

+ 4.275A + 0.3004

= wt% S x fs -

0.08

x 0.5 = 9.64.

9.6

SIEVERTS LAW

Gases dissolve in mohen metals readily. The gases like nitrogen, hydrogen, arnrnonia and oxygen do not dissolve in metals in molecular forns like

{Hz}

These howeter dissolr,e by dissociation of their molecules as

113

[Hz]

(e.6e)

(e.70) {Hz} = 2[Hl (e.71) + or lNHsl = [N] -3[H] The dissolution behaviour of diatomic gases like Nz, Hz and Oz can be illustrated by the exarple of hydrogen as shown in Eq.(9.70) above. The equilibrium constant of this reaction

shallbe

*"= *
K

(e.721

Assuming Henrian behaviour and equating fugacity with partial pressures

= *u -

fwt%Hzl
PHe

(e.73)

or the amount of hydrogen dissolved in the metal is given by

[wt%Hf =
lwt%Hl2

KH

PHa

or the arnount of hydrogen dissolved in the

netal is proportional
(e.74)

cr(pHJ

Sinnilar equations can be developed for oxygen, nitrogen and such other diatomic gases.ThiswasfirstobservedbySievertandhenceisknownas Sievert's Law which states

that 'the solubility of diatomic gases in metals is proportionaltothe under root of partial pressure of the gas in the ambient atmosphere' and is stated as (e.75) for hydrogen twt % Hl = KH (Pu, )"' (e.76) (prur)tz for nitrogen [wt %Nl = Kr'r (e.7n for oxygen [wt % O] = Ko (po, )tz phase is metal It is clear from the abow three equations (9"75) to (9.77) that if the brought in equilibrium with pure diatomic gas at one atmospheric pressure at a certain
temperature then the solubility will be equal to its characteristic constant as

I'ttl lo Hlt atms =

Kg

(e.78)

Now since solubility increases with temperature these characteristic constants are expressed as a function of temperature as

logKn=-tT'' or
tog Kx =

-1.246

(e.7e) (e.80)

'u+o

1.68.

and trom these the values of characteristic constant i.e. solubility values under pure gas at one atnnsphere pressure at any temperature of interest can be calculated and from this in

tum the solubilities under any other conditions can be calculated. Examples 9.3 : Molten alloy steelwas found to contain 10 ppm hydrogen when inside the fumace where the ambient partial pressure of hydrogen was 0.2 atnns. The steel must contain only 1 ppm before it solidifies. To what vacuum pressure it must be exposed before casting? Solution : The Sievert's laru'gives
[rad

%H]seel

Ku

pk"

and putting values

or

1 ppm =-0.0@1 wP/oHz

Ku=2.2x10-2 When 1 ppm is the limit 0.0001 = O.OZ2 x

0.001 =Knx(0.2)18

Pkz

114

or
or

pk,

P=2.06rt10-s dt.*. The vacuum should be better than 4.5 x 10 atmos. Exanple 9.4 : Find outthe anpunt of nitrogen dissolved in steel melt in a Bqssemer process
of steelmaking in which air is blown for refining the bath. Later argon was bubbled through the steel bath to reduce this nitrogen to 40 ppm for better solidification. Find out the amount of argon bubbled?

fqgj I v,v1z.

Giren

lof

Kr.r

=-

# -'12$
1.26 = 1.346

Solution : Assuming the temperature of the steel at the end of refining as 16000 C. The value of KH cornes out to be

tog Kn
KN

- - ---l!9-rc =
0.045

% nitrogen dissolved in the steel bath will be that what is in equilibrium with air i.e. with ptrt = 0.79 Therefore [%N] = 0.045 x 0]91/2 = 0.040 = 400 ppm This is to be reduced down to 40 ppm. lt means that 360 ppm are to be reduced, or nitrogen % be brought down from 0.04 to 0.004. Let us find out the nitrogen partial pressure in a gas phase in equilibrium with 0.004% Nz in

X::k

*,", ;.:;,Jffi["
0.00036
28

;ffij";":ff:PA=1-0'29=O'71
x
103

The anpunt of nitrogen remorred per tonne is = 0.00036 T/ ton steel bath

22.4at = 0.28 m3 at STP

Equivalent argon volume shall be = 71129 x 0.28 = 0.68 m3 at STP. Therefore per ton of steel bath nearly 0.68 m3 argon gas will have to be bubbled to scavenge nitrogen from the bath provided that errery time equilibrium is reached with the argon

bubble.

9.7

CONCLUDING REMARKS

Solutions are by tl'lemselves a category of materials possessing their orvn thermodynamic properties as distinct from those of their constituents. lt is because of this reason that a separate branch of solution thermodynamics has been evolved in the later half of the present century to understand the behaviour of solutions. The basic nature of solutions in the form of their models have been dealt with in this chapter and the finer properties shall be dealt with in the next chapter.

115

CHAPTER 10

SOLUTIONS I I mixing and excess functions, and regular solution

10.1
INTRODUCTION

lf pure silicon and silicon dissolved in iron, under similar conditions, are separately oxidised by identicalsurroundings, willthe free energy change per mole of silicon in both cases be the same? lf not why not? The answer is that the two values of AG can not be the san. lf these are not the same then the free energy associated with the reactants
i.e. silicon in two different forms, pure in onei'case and inpure in the other, must be dissimilar. These two values have got to be different because these are different systems of the same material, under similar conditions of pressure and temperature, and hence .associated energy will have to be different. lf these were alike very anamolous situation can arise. Fact is that these are not alike. Such situations are met almost always in metallurgical field.

Nowthereforethe difference in free energy changesassociatedwiththesetwoare

required to evaluate the net free energy change from pure to impure form. The essential difference between these two processes is: dissolr,ed in iron + oxidatiix + silicon oxide The situation shall be complicated further if instead of formation of pure silica, a silicate is formed. ln that case the proqNss (2) will be further modified by addition of the step silicon oxide + reaction with base + silicate at the end. ln process (2\ tree energy change associated with the formation of solution of silicon in iron and that of silica in base matrix are additionally required in assessing the overall change.
'

(1) Pure silicon (2) Pure silicon +

oxidation

silicon oxjd

The energy associated with pure element at any tempeature is merely enthalpy by way of its having been heated above the absolute zero temperature. But as solution the free energy of formation of the solution from the constituents is required. Pure elements do not haw any free energy at absolute zero temperature because pure elements do not have any enthalpy and entropy at absolute zero tempeature. The free energy of fornration of solution, which is often not at all negligibly small, has to be determined. lt is often referred to as the free energy of mixing or free energy of formation of solution and is generally expressed by the syrrbol AGM , with M as the superscript to indicate the mixing nature of the process.

1O.2 FREE ENERGY OF MIXNG

When to a large amount of solvent or to a solution, if a gram mole of another cornponent is added, the free energy change of this process is the molar free energy of mixing or integral free energy of mixing and is designated as :

AGM

(pure components) = G lsoturion; - )' "' = (NrGr * NzGz +...+.NiGi) - (Nrc? + NzGS + ...+ Nic,! (10.1) = Nr (Gl-c?) * Nz16z-c$ + ... + NiGi-eP)

where G

is the partial nplar free energy of component i and

Gl

is tne molar free energy of

the chosen standard form of the i component. The generalised entity @ i- Gf ) is known as partial molar free energy of mixing or relative partial molar free energy and often denoted
UV GJU

and hence Eq.

(1 0.

1) reduces down to molar free energy of mixing as

AcM = grGt + NzGl +....+

on the same lines all other extensive properties can

r.rielil)

(10.2)

be evaluated as : rui-#)
(10.3) (10.4)

molar entropy of mixing

asM =

(N1

sl" + NzsI

+...,+

or molar enthalpy of mixing

AHM = (Nr HY + Nz HS + ., .. + ttiHlu) and so on. It can be mathematically proved that as the thermodynamic relationships hold true components, relationships of similar format hold true for mixing functions as well: For total frce energy of solution
and partial nplar free energy of

for pure

AGM= AHM-TASM ifr component

(10.5i
(10.6) (10.7)

or

AGJl'l= aHi -TaSi aGlu = RT ln a

6 i different from Gf has been explained in Chapter 4 in Fi9.4.1. This difference emanates from the fact that the dissimilar atoms interact and alterthe short and long range ordering and hence, this change in bond strength is seen in the form of absorption or release of energy during the
The concept of a component in a solution having energy parameter

solution fiormation, i.e. the dissolution process. Obviously the Gf will haw to be different from G i . That is why for dissolution reactions like e.g. silicon in iron
<

Si> =

[Si]rwez.

(10.8)

AGo
that is and for
<

AGrezsJx

C> = [C]rwtz

-28000 + 5.54 T = - 17620 callg.mole

(10.e)

AGo = + 5400 - 10.1 T and hence AG?ezsox = - 13500 cal/g.mole It only means that the dissolution process would make them more stable in solution form by liberating energy during the process of dissolution. lt would be interesting to note that although the boiling points of both sulphur and phosphorus are too lorrr, a considerable amount of both of these can remain in solution in molten iron even at such high tempera117

ures

changes associated with their around 16000 c. This is because the free energy their strong interaction with eren molten ctssolution procass are qulte negatire, because of

im,

and hence the observed results'

10.3

IDEAL MIXNG OF GASES

Gases form solutions at

the entire composition or molecules dominates over unlike ones the range. \Mren the attraction between like atoms rray be more' chances of reaching solubility limit at certain concentration

space concentrations because of free inter-molecular orrer solutions form do some metals availabletoaccommodate molecules of othergases' composition over partial range, both in liquid and solid state, and many

all

Whentwoidealgassmix,becauseofeachbeinganassemblageofvolume]ess between two ideal gas particles' consenon-interacting particles,lh"r" are no interactions
or enthalpy quenily no bond changes, and hence no heat of mixing zero' is and hence the enthalpy change on mixing that In Sectlon (4'4) and Eq'(4'58) itwas shown

of mixing shall be available

Gi = Gf + RT ln Pi
and since Pi

Dividing by T and differentiatlng with respect where P is the total pressure of the gas mixture. to temPerature gives

P therefore 6i = eP + RT ln Ni + RT ln
Ni

(10.10)

a(GifD

temperature vanish' the latter two terns being independent of From Gibb's-Helmhottz equation

- a(Gi^) AT-AT

(10.11)

dG/T)

eqrialto partial molar enthalpy of the is component ln otherwords the pure phase enthalpy is to the total enthalpy of unmixed components' or the entharpy of the gI" tiout" is'equal (10'13)

O(Gi/r) Hf or E ar ro aT =7 aT T"
n,H,

nfl =

Fi

(10'12)

tnotherword" aH* = )'

- )'

ni HP =

or there is no change in enthalpy on mixing

as qualitatively and logically indicated above'

pro""r*. Earlier the particles had the process of mixing itsetf is a natural total volumes, and now have randomness over or randomness within their cnrn pure'state + ve rernaining constant)' the as is definitely volume of the solution (assuming pressure quantity and hence AG is -ve quantity' is giwn by Free energy of mixing df idealgases
AGM

Thefreeenergyofmixingofidealgaseswillhavetobeanegativevaluebecause freedom to rnove

=G

lmkture;
il

- G lunrvlixedcomponents)

=
Pr.rtring Eq.

S' lt1

niGi

-) H1
RT ln

niGf
Pi

=
AGM

niGiT' Lt1

cP)

(a.58)

i = Gf +

).l

",

nr

rn

(10'14)

118

and if mixing is carried out at constant pressure then

AGM

= ),

Therefore
andsinceAHM=

"'

RT ln

Ni since - T ASM

f.fi

=F

(10.15)

AGM liueatgases)

0 thus

AHM

Alsotherefore ASM=

-g=I

=-TASm )' ni RlnNi Ltt

(10.16)

)' n; R ln pi = 41
lf the gases are imperfect

(10.14

then in stead of partiaipressuresfugacitieswillhaveto be taken into consideration and the deviation from abow relationships shall be evident.

10.4

IDEAL CONDENSED SOLUTION

It has been shown that for any soltltion

AGM

G(solution)

Glpurecomponents)

= )' ./41

(GP

(cl + RT ln pf) + RT ln pi) -.)i Z.r1

Lt1

!' RT tn 4 = = Zt1 po

T'

RT ln

ai

as in Eq.(10.7)
(10.18)

rhererore on'==*ll,f ',rl"T'.",ir*'n'; ; i.*-1i] ," "',

By definition for an ideal solution obeying Raoult's law do not interact andthe Eq. (10.18) reducesto

a = Ni as the different components

Ni ln
Ni)

AGM

= RT(Nr ln Nr + Nz ln Nz

+ ...'.+

(10.1e)

Now

since -

ASM

o"'"""j'::;

" l#]

r.e. Aifferentiating the Eq.(10.18) with respect to tern-

= R(Nrrnar+ Nzrnaz+,,...+ N rn a)+ Rr

ASr AHM Now since (10.18) and (10'20) givas Eq. from and substituting in this the values

N,{iF).. ;- f#*)I = ldM + T

-

[-, 1op;

(10.20)

AHM

= RT (Ntlnar + Nzlnaz + ......Nilna;)

RT(Nrlnat

Nzlnaz

'.

[*' ffi) . N, (sF) - *, ffl] + - (iF)] = -Rr2 [*, (3p) . N, (3F) .

..
Nirna)

Frrz

ttottt
t'orrr

since the first two terns

fn 6e iignt

hanb side 'cancel each other.

119

An ideal solution activity is equal to mole fraction and which is independent of temperature,
and hence all

the

rs

aHM fideal) 0 wls obtaEned for idealgases earlier in Eq.(10.13). Obviously

ffi

terms.shall be zero and therefore

'

(10.23)

ASM6a.al=-pl (Nrlnar+ Nzlna2+....+

ASld(ioeat)=-RlnNi
AGM liaeatl =

N;

lna)

(1o.241 (10.25) (10.26)

=-R(NrlnNr + NzlnNz+.... +

Ni lnNi)

and partial nnlar entropy of mixing in ideal solution is therefore

Altematively the same is proved by Eq;(10.19). and hence partial molarfree energy of mixing in ideatsolution is therefore
(10.28) AGld tia".rl = FIT ln Nt On the same lines if (Gi - GP) are differentiated with respect to pressure, which is equal to volume change, then it can be pror,ed that

RT(NrlnNr

NzlnNz +

..,. +

Ni ln

Ni)

(0.2n

Vi=Vf or Vf-Vi=O
observed.

(10.2e)

that is the volume change on ideal solution formation is zero or (10.30) AVM 6aeat; = 0 lf at this stage Fig. 4.1 is recalled then, if the solution formed is ideal no volume change will
be
,

10.5 REGUIAR

SOLUTION

The concept of an ideal solution is only a concept and seen to be folloryed in practice only exceptionally. The actual or reai solutions arelar out from ideality. While studying the behaviours of a large number of solutions it was observed that although the enthalpies of formations of solutions are widely different their entropy of solution forrnation are not all that widely spread. ln fact in many cases it was observed that the entropies of formation

of solutions are just about the same as if they behaved as ideal solutions. This is logical enough because the entropy is essentially a configurational property and depends on freedom available for the particles for their movements. \Mren a solution is formed, whether ideal or non- ideal, the freedom available is practically equal to the total volume of solution available and it is almast the same for many solutions, since the volume changes on solution formation being generally negligibly small. This is the reason why ASM fideaD is
seen

to

be nearly the same as ASM

1reat1.

Based on the above observations, Hildebrand and co-workels introduced the concept of 'Regular Solution'as in way between the ideal and the real solutions. By definition it means that'in regular solutions the entropy of fiormation is equal to as if it was an ldeal solution'. Therefore by definition as derived earlier in Eq.(10.25) (10.31) ASM6egl = ASM(ideat) = -R(NrlnNr + NzlnNz + ....+ NilnNi)

Therefore

Hencepartialmolarentropyofmixingofregularsolutionis ASld holrever the AHM (reg) = whatever finite value the solution has:
AGM (reg) is given as

-Rlni

(10.32)

120

AGMl,'sy = RT(N'lnar + Nalnaa +...... + Nilna) sameasinEq.(10'18). Hence the partial molar free energy of mixing of a regular solution is
combining these with the equation giving entropy change gives

aelil {reg) =

AGI\rr

{real) = RTln a

(10.33)

AHM=AGM+TASM

=RTI(Nrlnar+ Nzlnaz+" ""+ Nilna)-RT(NrlnNt + NzlnNz + """ + NilnNi)l or lnl;=lnai -lnNi andusing E=Ni xYi iHMt"gl = RT(Nrlnlt + Nzln12 + '" '+ Nlln;yi)
obviously giwn bY

(10.34)

(10'35)

partial molar property is Since this is the total soiution property i.e. integral propefi the

lFld = RT ln yi
10.5.1 AtPha Function

(10,36)

it was While analysing the results of activity coefficients of various binary solutions

was substantially constant and was therefore called as ,r'nt?,,, found that the factor (1 - Ni) function. lt can thus be put

ct

as
ln

.r =

that for a binary solution of components 1 and 2. lt was also obsened described as onlY cr and
therefore
or

1fty
ln

and * z =

ffu
cr

(10.33)
cr

t=

and hence

* lnr,l
ln

Yz =(1 - Nr)2 1t- Nz)z

vt

(10.38)

yz

NE

(10.3e)

N?

putting Eq(10.36) in this gives

Ne (10.40) ^HY AHlt N? are inversely proprotional to the square of their log-activity-coefficients ln other words partial molar enthalies of mixing'ln atordmole fraction or also inversely proportionalto their one of the above fact it is a test, if experimental iata fit'in into a pattern where a regular solution therefore relationships are oUeyed, the solution is a regular solution' For of components inrrclved but the free energy is as for a real solution in terms of activities enthalpyandentropyaredifferentasshownintheequationsabove.

hYdl" yr

Example 10.1

"t added whereas in the other a mechanical mixture of Au+Ag was added' The difference was C' Find out the enthalpy of formation in temperature drop of tin in these two cases was 0.5o this value of enthalpy of mixing temperature of Au-Ag alloy at 70:30 composition. And to what of Au-A! alloy refer to? ls it 0o , 2500 or any other temperature? Given is-sp.heat of Sn-Au-Ag alloy = 0'03 caV0o/g alloy
121

: An alloy of sn-Ag-Au was made by addition of Au and Ag of total 5 grans case an alloy Au-Ag (7O% Au and 30% Ag) Oo C to a 95 gr"* *olt"n Sri ai 2500 C' ln one

Solution : The process of formation of the final alloy can be imagined to occur as Alloy (Au'Ag) + + Sn * alloY (Sn'Au-Ag) Process I Mixture (Au+dg) + + Sn * alloY (Sn-Au'fu) Process II The difference in these two processes is only as if the alloy Au--Ag is de-formed into individual elements Au and Ag then added. The AHM of Au-Ag (70:30) shall thus be additionally required when alloy is added to make up the final required Sn-Au-Ag alloy product. Conversely it can also be imagined that the alloy Au-Ag is formed first from the mechanical mixture and then added to make both the processes the same. ln that case the AHM of Au-Ag alloy shall be liberated and shall be available for heating the final alloy. ln other words the finaltemperatures reached are not the same. lf the finaltemperature reached is say f C in one process, which has to be belcw 2500C,thenintheotherprocessitwillbeT;0.5oC, The thermodynamic process offinal
alloy formation can be imagined to occur at 0o C in either case, Hent e

Hence

- AH (process ll) = AHM (atlo1{+-As} Cp dT(processll) = 6gM @[oyAu-As) Cp dT(process,) -4.

AH
(process

fl.t't

cp dr(D -{

cpdr(ll) = 6sM @rovAur--Ag)

ln either case the net change shall be

AHM lattoyAu-Ag) =

This is because the total enthalpy change has occurred in 100 gratns of the final alloy. This is also equal to the enthalpy change that has occurred in 5 grams of Au-Ag alloy formation in the sum total process. The 5 g Au-Ag alloy has 3.5 g of Au and 1.5 g of Ag or it is equlvalent

- C x 0,5 = - 0.5 x 0.03 = - 0.015 cal/ g wt of alloy Sn-Au-Ag = 0.015 x 100 = - !.5 cal/100 g wt of alloy Sn-Au-Ag

3.5* to 1g7

1.5 10g

g atoms of

Au and Ag respectivelY.

The totalg atoms in the Au-Ag alloy

or

= A.A177 + 0.0138 = 0.0315 g atom alloy 4760 cal/g mole alloy Au-Ag AHM = 0.0315 = =*=

This value of enthalpy of mixing referes to 0 C only because the process has been carried out in such a way that its value at 0 C has come out as an answer. lt can not be at any other temperature in this instant case.

10.6

EXCESS FUNCTIONS

The excess thermodynamic function has been defined as the difference between

thepropertyofrealsolutionand that if ithadbehavedasanidealsolution.Thus extensive property zo" M H ,U, S, A, G, etc.)

the general
(10.41) {10.42)

Z'" =

Z(real solutbn)

Z(ideal soslution)

lf free energy is taken as an illustration then

Gr = AGM lrealsol) - AGM (idealsol)

122

Putting their values as calculated earlier gives

G*" = RT {Nr lnar + Nalnae + .......+ Nilnai) - RT{Nr lnNr + NzlnNz + .... + NilnNi)

(10.)
(10.44)

=RT{Nrlnyr+NzlnTz+
= RT Lr'
Ni ln

+Nilnli)

1i

can be obtained by differentiating the excess free nergy that is the aborre The excess entropy 'i equation with respect to temperature ts AG: i dT and from this the excess enthalpy Ho can be evaluated as before. The excss property can be imagined in the form of volume from Fig. 4.1 in Chapter 4 as the difference between the dotted line and the solid line in (d).lt may be + ve or - ve as the case may be. This excess consists of contribution from each individual component of the solution as shown in Fig. a.1(c). This is known as excess partial molar component and is denoted
UV

ff

and can be written for fiee energy as

=xs h- r\:i =RTlnYi

(10'45)
(10.46)

For a solution therefore

Gxs

= NrGf + NaG" + NsG" +.....+ NiGi'"

The excess partialquantities are also interrelated as

Gi'" = nl'"

- rsi'"

fi0.42)
asshown

For a regular solution since

ffiSsl = RT {Nr lnyr + Nzlnyz + .....+ Nilnyi)

in Eq. (10.35) and therefore

or

Example 10.2 : Calculation of various properties of solution: lf activities are known then various mixing functions can be calculated at any temperature as follons: Given : The activitias of Zn and Cd in an alloy at Nzlr = a'4 are 0'3 and 0.65 respectively
at 5o0o K.

G"" = AHM lreg; Gi'" = AHlut"s) = RT ln

yi

(10.48)

lf Nzr = 0.4 then Ncd = 0.6 in a binary solution.

Hence I

G$0" = RT (Nzn ln azn + Nca ln aca) = 1.987 x 500 x 2.303 (0.4 log 0.3 + 0.65 log are =

0.6)

lf the same solution was ideal then

782 cal/g mole

lG$arl = FIT(Nzn.ln
=

Nzn + Nca ln Nca)

668 ca/g mole hence the excess can be calculated as

^c- = l1;_^il.,
= - 114 caUg mole partial properties can be determined as The
123

z. = RT ln aTtr =

1'987

500

2'303

x x

log 0'3 log 0'6

and

AGca = RT ln acd = 1'987 x 500 x 2.303

= -1196 caVg mole

= - 428 cal/g mole Now to e\raluate partial excess property of each component AGzn (irleal) = RT ln Nzt=0'4 = - 910 cal

lGca (ideal) - -507 AGli = lG zr - AG a (iiear) =

1196

910 =

286 cal

Now *"""" Now

similarly Then

AA{i = +
y

79cal 0.4/0.3 = 1.33 and Y cd = 0.65/0.60 = 1.0.q zn 'GM = f,"s) = - n1rutr.r ln Nzr + Nca ln Nca) = ASM (iuea1 - 1.987 x 2.3O3 x {0.4 log 0.4 + 0.6 log 0'6)

=_- 1.33 cal/g mole/Oo AE zn = - RT ln Nzr = 1.987 x = - 1.82 cal/g/mole/oo AS 66 = - 1.01 -do--

2'303

log 0'4

H$s can be calculated as

AHUg=lGHs+TASHs
knowing only one It would thus be very clear that how the mixing functions can be evaluated then the activities known properties are excess or parameter like activity. conversely if mixing

782

500(-1.33) = -1447 cal/gmole

or the activity coefficients can be calculated'

10.7

CONCLUDINGREMARKS

are respectively The free energy, enthalpy and entropy of formation of a real solution by, in givenbyEqs.(10.18),-lrO.eo1 and (10.22). Similartytheseforideatsolutionaregiven for regular solution are the sanp order by Eqs. (10.27), (10.23) and (10.25). The same

given,inthesameorder,byEqs.(10'18),(10'35)and(10.31)or(10.25). is given by The partial contribution of free energy of formation of ideal solution ideal solution Eq.(10.28) and of entropy byEq.(10.26);thepartialenthalpycontributionfor Similarly given Eq'(10'18)' by is solution offormation of regular being zero. The free "n"rgy by Eq.(l0'31) t'e' Eq' for regular solution enthalpy is given by Eq.(10.35) and entropy given as of freeenergy by Eq' (10'33) ' (r o.zi) The partiil contribution in regular solution is enthalpy by Eq.(10.36) and entropy.by Eq'(10'32)'
and partial part The excess lree energy of formation of solution is given by Eq.(10'43) by Eq.(10.a$. and these The energy changes on solution formation are by no means insignificant taking in changes energy arise lrom contributions of individual components because of the when the behaviour differs them individually, Such partial properties and excegs properties, of solutions' thermodynamies from the ideal one, do contribute to our understanding of the

124

CHAPTER

11

SOLUTIONS - Iil Applications of Gibb's-Duhem equation

11.1

INTRODUCTION

The concept of activity of a component in a solution as influenced by the presence of other constituents has been discussed in the previous chapter. lt has also been seen that although the practical solution may be multi- cornponent, their properties are mainly estimated from the knowledge of coresponding binary and ternary solutions. lt is easier to study and carry out measurements of thermodynamic parameters on binary and ternary

ments, vapour pressure measurements and so on, to measure activi$ of a component in a solution. ln a binary solution if activity of a component is measured then mathematically that of the other component can be computed without carrying out the actual measurements, Even if actual measurements are carried out even forthe second component mathematical evaluation can be used as confirmatory test ori the actual measurements. lf by measuring activity of one and detgrmining that of the other by mathematical computation is possible the process can be repeated with more complex mathematics to compute the activity of the third knowing those o(he two in a ternary solution. The proce.ss can continue for higher order solutions. The accuracy of calculations however does decrease ! with this progress.

solutions. The most commonly measured property of a solution is the activ1y of their components. Several techniques are available like chemical measurernents, ernf measure-

The activity is direcily related to energy as dd ; = RT ln a as per Eq.(4.69). Therefore even energy properties can be found out for second component when that is
known for the first.

The methods of these calculations are described in this chapter.

11.2 DETERMINATION OF PARTIAL MOLAR

PROPERTIES

The Gibb's Duhem equation for an extensire property of a binary solution of components 1 and 2 is given by

Nr

dZr + Nz d2 z = 0 where Z is any extensirre

=

property. lt means that

(11.1)

d7t

-#

oZ,

This can be integrated provided the variation ol Ez with composition is known for component 2.ln a binary when concentration of one component is known 1 - Nr shall be the concentration of the other component Nz . The integration can be carried out over the limits to be fixed. Thenaturalchoiceisof lcnryerlimitasthatwhen Nz = 0 i.e. Nt = l ordZt= 0 and the upper limit is that when Nr = Nt at which the dZ r is to be found out. The integration of Eq"(11.1) thus gives

Zr (Nr - 1) =-{,:i' or Zt (Nr - Nr) whenNr=12=Qand *' Nz .therefore Zr (Nr - Nr) = - t'r* azz = 'Nt
1

'Nt -

Jtlr

- tJr
1

.dZt

-l"Nr -

,flr

- Nr
1

dZz

(11.2)

.
t

ffioz,
(11.3)

concentration. This is illustrated below with the help of an example and the calculations involved therein. Example 11.1 : Let us assume that the follorruing data were obtained for partial molar energy of mixing of Ag-sialloys at 1150o C. Nsi 1.0 0.9 0.8 0.7 0.6 0.5 4.4 0.3 0.2 0.1 00 6 si 0.0 90 12O 28O 400 5s0 800 1150 1400 1800 0 cal/mole. Let us saythat partial molarfree eneregy of Ag at 0.2 atomfraction is required to be computed. ln the equation (11 .2) or (11 .3) component 1 is Ag and 2 is Si. lt therefore reduces to :

This integral can be solved graphically to compute the value otZ

at Nr = Nr

fx tNes-1

Jllag = o'z

dGlo = |

J\las

o'2

x
t

"Nes-l

ffioGs,

or this will reduce down to

oGm= - o.2 =

flon=o'z x - tNon-1

The available data will have to be processed further as

ffi cGsi

Nsi 1.0 0.9 0.8 o.7 0.6 0.5 Nns 0.0 0.1 o.2 0.3 0.4 0.5 e.o 4.a 2.33 1.50 1.0 -NsL Neg Gsi 0 90 12O 280 400 550
A graph is plotted with G si on the x-axis and the ratio

0.4 0.3 0.2 0.1 00 0.6 0.7 0.8 0.9 00

0.66 0.4! 0.25 0.11 800 1150 1400 1800 0 cal/mole
Nsi

The area on the graph under the burve and bound by the x-axis between the limits Nns = 1 to NAs = .02 is shown by thatched marks. The area can be worked out graphically but since
it extends in the form of a tail to

ffi

on the y-axis as shown in Fi9.11.1.

ln the present case it comes out to be 2118 caUmole and hence the partial molar free energy of mixing of Ag at Nns = 0.2 is - 2118 cal/mole. The values of GXs at various concentrations can be computed likewise for each composition separately, by computing each time the area as above.
126

- m i.e. asynrtotic form, it can not be determined

accurately.

Nsi No* 4

SHADED AREA =

dr=

o.z

--2118 cat

300
Fig.
11.1 -

600 900 , 1200 1500 '-"+ a,G^. -M Cat/G.Mo[e

t800

2t@

Plot to evaluate the Gibb's-Duhem integral for evaluatian of

Partial molar ProPertY.

11.3

DETERMINATION OF AC'IIVITIES

ln the case of binary solutions it is experimentally readily possible to determine

activity of a component, particularly the solute, in a solution using a varieties of techniques but it is rather difiicult to determine experimentally the activity of the solvent component at the same composition.This difficulty is more pronounced in the case of dilute solutions' The integration of Gibb's Duhem equation comes out handy to determine the activity of the other component, usually the solvent, when that of the solute component is known by actual measurements. lt has already been seen that activity is nothing but a function of partial molar free energy and hence the method of integration of Gibb's Duhem equation in the previoris section should be applicable for estimation of activity as well. ln this case the Gibb's Duhem

equation is to be transformed into an equation correlatingactivitiesof thetwocomponents in a binary solution. By taking partial molarfree energy as the extensive property the Gibb's Duhem equation can be written as :
dG 1 = RT dln ai and dividing by RT Putting Nrdlnar+Nzdlnae=0 and gives eliminating natural logarithm Nt dlog at + Nz dlog a2 = 0 and

NrdGl +'N2dGz = 0

(11.4) (11.5) (11.6)

cor

dlog a1 =

T9
Nr

d log az
127

lntegrating again between the limits gives

Jllr * Nr

Nr = .l

at the lcnrer limit

Nz

to N1

Nr

as the uper limit

J*, -.,

drogal =
- Nr

ft-ru' - 'Nr 1

N1

q log a2

(11.4

or thus

(d log a1)x,

(d tog a1)p, = 1

=-

since when

Nr = 1, lt = 1 (d rog ar) = -

dl:)'
=
e

ffi

o,os

*
(11.8)

and hence log a1

- n.,. tne Nr concentrations. The.curve ap_ proaches at one end + infinity when Nr = 0 to - infinity when Nz = 0 at the other end. The difficulties encountered will be clear by taking a numerical example and solving it as follorrys : Example : Let us take the measurernents of actiMties of Ni in Fe-Ni alloys atl6000 C made by G'R'Befton and R.J.Fruehan (J.Phys.Chem.1967),which are shown in horizontal 'columns 1 and 2. Let us try to carcurate the activity of iron at Nre = 0.9"
integration is carried out between limits upto different

A graph plotted betwen Nz / Nr and log a and the area under the cune bound by the x-axis . over the range N1 = 1 to Nt = Nr is estimated to obtain the value of log ar N,

d::)'

ff

aros*

NNi 1.0 0.9 0.8 O.Z 0.6 O.S 0.4 0.g 0.2 0.1 aNi1.00.890.7660'62l0'485o.g74o.283o'2o7o.137o.067
now calcuhtgd va[res with lhe same columns continrcd

00

NFe 0.0 0.1 O.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 Nrui :9.0 4.O'.2.99 1.50 1.0 0.66 v'vv 0.4i| 0.25 0.11 v'D NFe log as - 0.0506 0.2076 0.4271 0.6940 "t.1739 0.1157 0.3142 0.5482 0.8664

0O

ln order to solve the integralthe data are processed to' obtain horizontal colums 3, 4 and F and graph is plotted with log aNi on x-axis and Nrui / Nr" on the y_axis as shown in Fig. 11.2. The area underthe curve bound by x-axis between the limits Np; = 1 to Nrui = 0.1 is estirnated as the value of the integral in eq. 1t t .8). lt is observed that the cune extends to - infinity when Nrui = 1 and hence required area has to be calculated stricily upto infinity limit. This is practically just not possible and hence the calculations are in enor. However with.all these errors the value of lob ape at Nre = 0.2 is equal to the area shown by thatchings and is equalto 0.85.

11.4 ESTIMATION OF AOTIVITY

COEFFICIENT

lf activity can be intenelated through Gibb's - Duhem equation, activity coefficient must also be similarly intenelated. As derived in the previous section in Eq.(11.a)
Since in a

hence
it also

binary
dNr

Nt

dlnar + Nzdlnaz = 0 Nr + Nz = 1

dN2

alteringthefornssuitably Nt

means Nr d ln Nr + Nt d ln Ne = 0 fromdefinition e = Niyi i.e. log a = log Ni + log y;

128

# * ruz ff

I
a
7 a

-N*r

(tR e SIIADED ARSA AGTIVITY OF Fe (o& N6ro)r o.!5

LOG

Nros
4
I

04
Fig. 112

05 0'6 LOG O

0.7

08

Graphical determination of activity using the

G ibb's

- D uhe m inte

gration
(11.e)

or

log

Subtracting Eq.(11.9) from Eq.(11.4) leads to

a-

log Ni = log yi Nz dlogy2

Nr dlogyr

(11.10) (11.11)

dtogyl =
As before integrating between the

- #f
-

dlos12
1 to

'Nt-l
(ros yr)Nr

J,lr

- Nr

limits Nr =
J.,lr

N1

OlogYl =

- Nr | JNr-l

Nr
Nz

N1

ologY2

(11.12)

Nr

- (rog y r) = - d] :)'
=

Sinceat Nr

= 1, t1 = 1 andhencef r = l andthereforelogyl =
(tosy r)r.rr - Nr

ff arog*
0 (11.13)

therefore

- .(:: )'

Nz

NI

o logY2

This can be solved graphically by plotting Nz /Nr vs. log T z and the area under the curve bound by the x-axis between the limits Nr = 1 to Ni = Nr shalt give the value of log y r and from which y 1 can be calculated at Nr = Nr . Such values at any other composition can be calculated likewise. Knowing y r, the activity values can be calculated through the

relationship a = Ni . y i. The activity data of Ni in Fe-Ni system at 16000 C shown in the previous section can be processed further with respect to Eq.(11.13) to understand the method of this calculation more precisely.
129

Bringing back the data here again

Nui 1.0 0.9 0.8 0.7 0.6 0.5 0.4 0.3 O.2 0.1 aNi 1.0 O.B9 0.766 0.62 0.485 0.974 0.283 0.207 0.137 0.067
0.67 o.7N 0.69 0.885 1"0 0.988 0.95 0.808 0.707 0.68 ,logyr* -0.0052 -0.053 -0.126 -0.161 -0.173 - 0.09 - a.azi - 0.150 - 0.167

00

il*l

Nre 0.0 0.1 x!i9.0 NF

A.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 4.0 2.3s 1.50 1.0 0.66 0.4i| o.zs 0.11

The graph is plotted with these datawith log y r'l on x-axis and NNi/ Nre on the y-axis. The graph ls shown Fig. 11.3. The activity coefficient of iron at 0.3 atom fnaction composition is equivalent to the thatched area on the graph and which is the value of the integral as desired

by Eq"(11.13).The area is equivalent to log y

re =

0.01186 and hence

Fe

1.31.

I fr (fftro'll = 9IADED
1fu =

tt

LOG tr{r Fig,I1.3 - Graphical ileterminatian of activity coefficicnt using G ibb's- D uhem inte gration
130
the

ll.sESTIMATIONOFACTIVITYCOEFFICIENTUSINCALPI{AFL|NCTION
From the Previous section dividing both bY dNz gires

Nr

dloglt + Nzdlogl2 = 0

as inEq'(11'10)
(11.13) (11'14)

N;

ohfry-*

m,ff= o
o*r

or

dros1l =

# .#
d ros vr =
ln Ni

As before this can be intelrated between the limits

JNr-1

f*Nr x

-{l:i' .

Nt = 1 to Nt = Nr gives {e9J3

ffi

6p,

(11'15)

By definition the term (1 - Nr)z binary solution and as has been obsened

is

the cr (alphd function for

yz

at
and u1=

vr -*' N3
ln

ln ano d2 = -:;
.

N,
ln

d2 = cL andhence

..

1r _ " = *i =
ln

yz
cr

(11 .16)

Na

and by processing this equation it can be shown that

logyi

J'lr = * a Nt *t -{,-;'

Nr

dNt

(11'17)

{t'"kdNr. tNe,.7

= SHADED AREA

U6.: O'OO2 ct Na'

t.q>lz

('lz

313

I
using Fig.11.4 - Graphical evaluation of activity coefrcient alPha-furcian.
131

ll

if o' 'i'e' log y z /(1 - Nz) is plotted vs. Nr the area under the curve bound by x-axis between the limits Nr = 1 and Nr = Nr cen be obtained and if from this computedvarue of -c Nr Nr issubtracted, the varue of rogyl is obtained There is no asymptotic shape of this curve and exact area can be found out to get the activitv coefiicient accuratery. This is shown in Fig 1r.e usin! section for activity of nicker to work out the activity coefiicient of iron at Npe 0.3. The ., = value at NFe = 0.3 can be evaluated. The value of the integralcan be assessed from the graph in Fig. 11.4 and is shown by shaded area' The above equation (11'1n can now be solved to work out the value rlt Nre = 0.'3 and from there the value of activity coefiicient of Fe works out to of log be 0.002 at iron atom fraction of 0.3.
there'fore

t;;';;;.;;';ilJo*""*

empirical equation then the second component.

Alternatively if activity coefficient of a component in a solution is expressed by an it can be proces'sed mathematically to get the activity coefiicient of

11.6

CONCLUDING REMARKS

by

thus very usefur in evaruating activity, its coefficient or any extensive property of a component in solution when that of the other compoenent is known over a range of composition. Atthough it is tedious but is usefut particulady when the measurmenets for the other component srv not accuratery rneasurable -"'F-rrYrrr lre
experimentation.

The Gibb's - Duhem equation is

132

CHAPTER

L2

EQUILIBRIA IN PHASE DIAGRAMS

12.1

INTRODUCTION

ln a single component system i.e. in pure substances the phases that can exist under appropriate conditions of temperature and pressure are the solid or liquid or gas forms of the pure substance, For a given amount of pure substance if P and T are fixed the volume is automatically fixed. Even if amount of substance is varied T and P are potential terms and hence decide the equilibria lndependent of rnass of the substance. The areas where each one of these phases exist are therefore available from T-P diagrams as shown in Fig .6"2"

The T-P relationships also indicate the conditions when solid- liquid, solid-gas and liquid-gas shall co-exist. This is confirrned from G-T relationship in terms of associated minimum free energy for the stable phase or phases as in Fig. 6.3, Although these relationships do indicate phases in equilibrium in a single component system, these are
not called equilibrium diagrams. Equilibriunn or phase diagrams however ryrean graphical replesentation of stable equilibrium phase regions that exist with respect to temperature and cornposrtlon in a system with minimurn of two components wherein at least one component is in a e,Pndensed form. The pressure is fixed at one atmosphere normally in plotting these diagrarse fhe equilibrium diagrams are often known in terms of the number of components inwlved irl the systern. lf only two components are present, it is binary equilibrium or phase diagrarn, if three are present it is ternary diagram and, if four, it is quarternary diagram and and so on. A binary diagram can be depicted readily as atwo dimensionaldiagrarnwith composttion on thex-axis and temperature on the y-axis. A ternary can be indicated in a trianguiar ir:rm as a two dimensional representation of the three dimensional situation at fixed ternperature' The

quarternary forrn is still complicated. ln a more thara foun, that is truely nnuitE-eomponent system, it is not at all possible to construct the diagrar"n as a lrariation of temperature and composition and hence for a fixed compositioll the phases are ascertained or it is reduced to a pseudo-ternary systern to be depicted in atriangular forrn,
The binary diagrams are by far the rnost populan useful, readily legible and available forms of phase diagrams. As apre|irnanaryintroductlc;ntothesubjectof energy considerations and' phase equilibria, the diseussion here is eonfined to binary phase diagrams
only.

A binary system eren in a condensed form may exhibit, one or two liquid phases, one or more solid sglution phases, one or more intermetalic or chemical compounds, one or more mechanically mixed phases as eutectics, magnetic and non magnetic phases, and so on. ln other words the diagram may depict regions of stabilities of several of such phasas. The simplest diagram with one liquid and one solid solution, where complete solid and liquid solubility between the two components exist, shall have the region of stabilities of liquid and solid solution phases andseparatingthesetwophase regions, a area where both phases co-exist ih equilibrium. There will have tc be a two phase region, separating two single phase regions. When one phasechanges to the other on heating or cooling, the gradual changeover through the two phase region is thus necessary and without this direct changeover from one to the other phase is jurst not possible.

The equilibrium diagram of two completely immiscible components even !n liquid state e.g. Pb-Fe, W-Pb etc. are of no interest because no,other phases, except the two pure component phases, mechanically in contact wiih each other,'existthere. Therefore phase diagrams where at least a partial liquid solubility of component, one in the other, is possible, are ofrelevance.Alternatively at least complete liquid solubilitywithoutanysolid solubility may also be relevant.

The phase diagrams are constructed using equilibrium measurements and subsequent phq:e analyses to be carried out by either chemical, X-ray, metallography and such othertechniques. Dilatornetric or differential graMmetric (D-G) or difierentialthermogravimetric (D-T-G) techniques are used to know. thetemperaturesatwhichphasechangesoccur. Those measurements are carried out overthe required temperature and composition ranges to completii the diagram. These measurements are carried out reversibly to ensure equilibrium" The fact that these are equilibrium diagrams means that they indicate the equilibriurn phases existing in a given tenperature-composition range under isobaric conditions with respect to the composition. The second law clearly establishes that for a system of definite composition at a fixed temperature and pressure, the equilibrium stable phase is the one which possesses lowest free energy. Equally true would be that when two phases coexist in this diagram the chemica!potentials, G i for a cornponent in the coexisting phases must be the same. Alternatively the activities of the same component in the co-existing phases must be the same since free energy and activity are directly related to each other. ln other words
the phase diagrams must show appropriate free energy composition and acltvity composition relationships in conformity with the larars of thermodynamics. The phase diagrans are evaluated by assuming cooling of certain composition of the system from where it is fully liquid. As this cools no change will occur till the temperature buches the liquidus boundary (above which only liquid exists). Every phase diagram nodd pose this situation. At the liquidus temperature, since by its definition, that solid phas shall seperate out from the liquid. The equilibrium inwlrrcd is Liquid

the pure component, a solid solution, an intermetallic conpound or a mechanical mixture of components known as eutectic. This will continue till all the liquid phase is transformed into solid. So the free energy of fornntion of one of
and solld phase can ,be almost
134

these solid phases, when minimurn give the clue regarding the seperate phase(s) or equilibrium phase(s) and the temperature range o\,er which it(these) shall be stable.
Similafly the soiid phase so formed on further cooling can undergo phase changes as *' two solids Solid Solution 1.

2. 3.

Solid

Solution Solid solution

{eutocbid change)

.'

another solid solution a liquid and a solid

As the above free energy or activity consideration shall apply to this and such other equilibria, involved in the given corfrponent composition, as it cools to alrnost room ternperature or even belor it if required. Any other ch'ange,s also can be treated likerryise.

ln order to correlate the phase diagrann withfreeenergies o{ component phasas and the relevant activity of conponents a fsru simple diagranrs are considered bela'v.
412.2 FREE ENERGY OF FORMATION OF SOLU'NON There are systens where complete solubility orer entire composition range in liquid shall exist. But many ceramic systerns iike alkaline earth-metal oxide-silica systerns exhibit only partial liquid solubility. There are many wher'e only one solid solutian exists over the entire composition ranges like Cu-Ag, Cu-Ni, Pb-Au etc. But many others exhibit only partial solid solubility at each end. ln the extreme the solid solubility is so negligibly smallthat almost pure component seperate out without any solid solution formation at each end" The pb-Sn is atypical system olthis type wherein the liquld freezes into afine mixture of Pb and Sn as eutectic of a certain fixed composition and the excess of any component as a seperate phase of that pure component. The evaluation of a solution phase thr.rs start with deterrnination of free energyof forrnation of a solution, initially in liquid state and then in solid solution form as well' The AGM, AHM and ASM for the fornration of a solution from components 1 and 2 have already been evaluated in Chapter 10 and can be reproduced aGueat =-TASiueat as = - RT[Nr lnNt + Nz lnNa] since AHiaeal = 0 for idealsolution. However if solution is not ideal i.e. ai * Ni bd a = y i Ni or hi = ii (wt%i) and AiM *; = AHreal - T ASreal hence ' The actual value of AGM depends on whether AHM is -ve or + \ i.e. exothermic or process. endotherrnic. But when solution fornrs AHM will have to be -ve, being a natural Since the interaction amongst the components manifeqt as -ve or + ve values of AHM, the
the actiVties of components shall show corresponding -ve or + ve deviation from ideality' lf all infornration is known the AGM can be evaluated for any composition of solution at any atrnos. temperature. AGM is therefore a function of temperature and composition ( prassure 1 fixed).

The free energy of formation of a solution is shown in Fig. 12.1 under varieties of 'C' is for the conditions. The curve at 'A' is ideal solution fornration and 'B' is for the -ve and definitely will + ve deviation from ideality. Depending upon the actual value of AHM , which
135

Fig. 12.1 - Free energ) of formatian of anidealsolution as afunctbn of compositian along-with those of real so-

lutions to

indicate the positive and

ne gative dev iatbn

from

ide ali 4t.

coMPostoN be related to interaction of components the real aGM shall_acquire the value as a resultant of
The fact that components form solution ,being

AHM and T ASM factors.

a natural process, is itself an indication the solution. aHM also *itt nr* to be -ve as the natural process is exothermic in nature. The ISM will however be a + ve quantity forthe same reason. Another interesting part is that the lGlv can be evaluated by drawing a tangent at the conesponding point of composition on the AGM curve, and the intercepts of this tangent as shown in Fig. 1 2. 1

of -re value of AGM for

liquidsolutionand upto whatewrextentitisso,thesolubilitylimitshall extend.The Fig.12.1 shows the state of affairs when liquid solubility is exhibited over entire range of composition. No.other form of phase, like say a mixture of compeinents 1 and 2 shall be stable. Ewn if the AGM of this mixture is eraluated its values would b* less -ve than the conesponding value AGM for sotution as shown in Fig..12.1.

onaxisatNr = 0 and Nz = O girethevaluesof n6lil andaGld.AtNr = 0 meansNz = 1 and at N2 = 0 means Nr = 1, the slope will harre to be minus infinity and hence the cune atthesetwo extremities mustbevertical since at Nr = 1, AGl/| = 0 and A@ = -o andatNz = 1AGI= 0andlG$r= - 6. The -ve AGM value for any such solution is a sure indication of the stability of

This can be proved from Fig 12.2 which i* reproduction of the Fig. 12.L for AGM as a generalised case, not specifically ideal or olti*.r-wise. Let us imagine a mixture of two solutions of composition 'A and 'B'with the cornsicsition average being formed at ,C,. The AG''' will be the total of AG of these two cornponent solutions as giwn by point A and B respectively' The sum total value shall be as depicted Uy C wnicfr is rnuch lorruer than (less -rre) point 'D' which gives AGM of solution of A and B solutions. Hence solution D is more

136

than mirdure represented by C' This holds true for entire range and
stable

?
I

i5

therefore solution phase shall be more stabler than mere mixture' Fig.12.3 gives the free energY of formation of solid as well as liquid solution over the entire cornposition range at three different temperatures for a system which exhibits solubility in both liquid and solid state over the entire composition range. The IGM for solid solution and liquid solution at temperature Ts and Tl
make interesting reading. At temperature Tl only liquid solution can exist in the

phase diagram. The values of AGU and

Fig.122 - Shows free energy of mixing

as it varies wiih compositinn

lG$ hare been plotted in Fig.1 2.3(b) . The

tive than those of A G$ vdues for anY solution. The phase composition, meaning thereby that liquid solution is stabler than solid indicate solid solution diagram confirms this. Similarly the argument for temperature I Ts shall axis cuts the to be the stable phase as shown in (c). At temperature Ts-l the temperature the diagram in composition vs. liquidus at 'b' and solidus at'c' as shown in (a). The AGM composition right of c, solid indicates that for composition left of b, liquid is stable and for the same and hence they solution is stable. ln-between b and c, both AG$ and AGF are of free energy co-eist. The phases in the diagram are thus confirmed on the basis
considerations.

for a solution

GU has allthrough values more nega-

12.3

SOLUBILIW FREE ENERGIES OF SYSTEMS WITH ONLY PARTAL SOLID

for such a The system is typically shown in Fig.12.4. The AGM of solid solution of formation of solid solution system is like that in Fig 12.1 . Let us work out the free enelgies the horizantal dotted line for the and liquid solution at various temperatures, as depicted by and solid solution p have been corresponding values. The AGM for liquid, solid solution a .b, between the compositions olotted at temperature Ts-t in Fig. 12'4tb|' lt is apparent that ;;;id phase has the toryest vatue * compared to aGM for .' and p solid il#;;;;il seen in the phase diagram' Also solutions and hence liquid phase is stable in this region as this region where * seperates the A G}l has lorarer value on the left of composition b as it is the precipitation of p solid solution out from the liquid solution. Similarry A G$ shall indicate
beyond right of comPosition c. AGM for .' - p solid solution It is equally clear that at Ts-t- in between b and c that p, are not stable phases in is more than that for liquid solution and hence o and individually
137

lJ1

COMPOS|TloN tL Nt

*[
rr"rl!

this region. As the temperature is lcnvered down belos Ts-l the miscibllity gap decreases and eventually at Te both o and p have AGM less than that for liquid and hence are stable. But for the region between 'g' and 'f ,

r3

both

aG$ and AGff are same

whereas for composition less than point'g' it ls AG$ . AGy and above

IAT
TL
I

TEMP

.li1
I

point'f AGy
and
B

IGS

inOicating the

cr

slability ranges at either end of

It
I

I
I

AGs

the phase diagram. lf temperature is further lcnrvered the overlapping

of a and p lines extend further thereby

decreasing the stability region of a

AT TElvIP

Tj

and p as independant phases. This is

I

obvious because of the slope of

cr

I
I

tg

f
,{-T

p) and F /{a + p) phases being sloping towards lower solid solubility

(cr

ranges.

TeM?l.rl
I

12.4" FREE ENERGY OF PURE

EUTECTIC SYSTEM

Fig.123 - Free energ)-composition relationfor varbus phases at different temperatures for binary systems exhibiting complete solid soltbility.
ships

Atypical pure eutectic system is shown in Fi9,12.5 (a). Let us consider the temperature which is between the m.p. of the two consituents as shown by the line T*+1ry. lThe conesponding free energy values,

AGU and AGU , are plotted in Fig 12.5 (b). Since temperature is belcrut
the m.p. of component 1 and since no solid solution is formed at 'a', solid -1

must precipitate out bn further cooling. ln otherwords AG$trl must have

a lower

value than

AGY. a tangent is drawn at conesponding point 'a' on the free energy curve the intercept will gire partial, in this case of pure component, free energy which is less than that of solution

AGr = A6lnl . This is qhown in Fig.12.5(c). At a larrer temperature Ts+1zy which is lcnarer than the lowest m.p. of the two constituent, the situation as shown in Fig 12.5(b) will qualitatiwly exists at the other end of the diagram as well.
as
138

I lltt

l".rl

F ig.I 2.4 - Free energ)-eornpositinn

'./

/r
I "

relatianships for various phases in a binary phase diagramwith

partial solid solubility.

:q

At temperature Te tne AC$ and AGr are overlapping on the left side of entectk composition i.e.point'E', meaning thereby that component 1 and liquid coexist and on the right similarly, component 2 and liquid solution coexist. lnterestingly the pure phase 1 k; unstable on right of eutectic E composition and similarf phase 2 is unstable on the left ol' E. lf situation at temperature Te and composition E is considered then AGU , and AGr shall
overlap on the left of

E and AGU , and AGz shall overlap

on the right of E to indicate thei

coexistence, which is the case, The AGr will be less -ve on the right of E and therefore beloit' AGF cune and AG! willbe less -ve on the left of E, and therelore below AGU cune ar is so obvious'in Fig.12.5(d) CONDITIONS FOR MISCIBIUry GAP IN PHASE DIAGRAMS

12.5 LIMI]]NG

When solubility exists in liquid state the AGf is always -ve, ls it is a naturell process. But if the constituent componehts show a +ve deviation fiom Roultian behaviour then theAGU vduesbecomeless negative and if the+ ve deviation issufiicientlylargrr then AGF

rpy

even have + ve values

orer certain range of composition. lt means there is lit

139

I I I

rl"e
t
I

2+E
,

I
I

I
I

Fig.125 - Free energ)-composition

latiorchips at v arious temperatures far a pure eutectic systefti vis-a-vis
re

the phase diagram.

I I I

Aor

'I

tt

FFu

l,

tendency not

form solution and exhibit liquid immiscibility in the region where lGf is + ve. The norma! convex downward peak of AGU ,when -ve, becomes convex upwards as !t is clear that for solutions of compositions 1a and
1u the

to

shown in Fi9.12.6.

AGU are the same since the tangent is sqme and hence must be coexstent in equilibrium. Thre AGU howewr increases beyond 1a with composition and after attaining a peak in convex upward form reduces to attain the maximum value at 'b' as shown in Fig 12,6(b). For any composition of solution between the points 'a' and 'b'the composition can be imagined as a mixture of two solutions, say for example as of 'd' and 'e' with the effective gross composition shown by 'f'. The aGU for composition 'f is thus that given by point 'c'. But as a .mixture its real value is depicted by 'f'. ln other words the system has tendency to exist as two liquids rather

than a hemogeneous solution having

of 'a" and 'b' are two liquids of cornposition 'a' and 'b,. on the left of ,a' and right of homogeneous liquid solutions shallexist as stable phases.

lG[ corresponding to point c because, free energy corresponding to point f is lourerthan that for'c'. The stable configuration between compasition
,b'

14

2\-

-qr

SF

7l

.|Y' .ot t
)'r
I

.t

!>
<t, s<
EF

I * l--*-+cOMPLET i. --* - j - :lrlMlSClBlLlfY

o-1.

l-'

tdl

EI

TENDENCY : TO LtbUrD : tHMt{ctErur*

rThlO

Itrouto lo ,?
rb

Fig. 12.6 'The free energl-composition relationships to explain the conditions when liquid immkcibility
becomes imminent.

The liquid misscibility gap is atways associated with a strong like-atomlmolecule attraction or + ve deviation from Raoultian behaviour. Mathematically it can be deduced that or O6/Ot,tr or O2g/ON? or O3G/Ctt? must all be zero for nriscibility to occur as composilion changes from one end to the other in a binary solution. lt means the phase diagrans musthave a liquidus, notvaryingintemperaturewith composition as shown in Fig 12.6 between compositions'a'and'b'. Also since activity is directly proportionalto free energy the activity also should either show no + ve variation with composition or it should not show any variation r.e invariance with composition. This is shown in Fi9.12.6(a) for

141

(o)

L2.

G+2

Fig. 12.7 - Free energt-composition re lationshftts shorv in g the s tabititie s of inte rme t allic c omp ounds.

!r-l

:, i eic

:..

c clc,

96z- cailPogt?toN

compositions between 'a' a!.id 'b,. That it should not show invense deviation at some Stage as it varies with composition goes without saying.

12.6

FREEENERGYOFFORMA-

TION OFCOMPOUNDS !N PHASE DIAGRAMS lf the components are such that their mutual attraction, in terns of their electronic structure, is sufficiently large then their cornbination
may resuh intheformation of acom. pound often intermetallic at a certain fixed composition. A typical diagrann representing this is shown in Fi9.12.7. As per phase rule, on either side of the composition of these compound must lie a two phase region.

The AGU at temperature it is apparent that over than solid.

Tr when erery thhg is liquid is shown in Fig.1 2,7(b) where the entire range of composition it is the liquid phase that is stabler

extend.Atastilllcnrer temperatureTs-r which is muchlowerthanm.p.of compound,itwill seperate out in the range of composition a-b beyond which on either side is liquid phase stable. ln other words the free energy graphs should show miscibility gap between
142

At the m.p. of compound Ci.e. at T both the AGU and AGU hare sarne value and hence both exist in equilibrium with each other. The composition range of stability of a compound will be between the two entectic points Er and Ez ovenrvhich liquid phase shall

composition a-b. The tangent shall be cpmmon to AGU and A eB nut there will be two solid-liquid equilibria on either side separated by a miscibility gap as discussed earlier.

12.7 CONCLUDINGREMARKS
It is therefore clear that the phase diagrams are nothing but the depiction of equilibria between composition and temperature{pressure being kept constant) and the nature ard stabilitim of various phases can be guessed from theirthermodynamic information like free energy of formation of the phases or the component activities and so on.

4i|

CHAPTER

13

EL ECTROCH EM I CA L PROCESSES

ennf measurements

13.1

INTRODUCNON

It is a known fact that compounds on dissolution in aqueous or fused media dissociate into respective ions. The conductivity of such a solution is due to the migration of these constituent ions, ln such a solution if a metal (more precisely an element), whose ions exist in the solution, is dipped, the systern now in the form of a metal in contact with its orun ions, acquires a potential arising out of an equilibrium of a reaction like

between the metal and the solution. This system is known as a galvanic element or an electrode. By virtue of the equilibrium of the above reaction, at the boundary of the rnetal and the solution, the metal part acquires a potential characteristic of its orvn and, dependent on concentration of ions (more precisely [s chemical activity) and the temperature. This is known as the'electrode potential'. Two such elements or electrodes when joined as, electronic to electronic and ionic to ionic conductor, becomes a galvanic cellwith potential as net algebric sum of the two electrode potentials. Cell is formed because dissimilar metal electrodes have different potentials. Electrochemical cells are thus of two types, v2. concentration and galvanic cells. Two dissimilar metal electrodes when joined make a galvanic cell and two similar metals but with different concentrations of the solutions around them, when connected, form a concentration cell. Asolution in such cells is therefore referred to as electrolyte. A typical example of galvanic cell is Daniel Cell with Cu/CuSO+ as one electrode andZnlZnSOa as another. Because the electrode potential is due to the reaction as mentioned above, the overall cellreaction in DanielCell shall be
(13.2) Zn+CuSOa=ZnSOe+Cu It means that Zn has a tendency to go in solution and eject Cu out of solution as stated above. Likewise in a concentration cell the natural process is tlrat the nretal ion from electrolyte of high concentration shall move to the lower concentration electrolyte.

-r

Mn* + ne

(13.1)

13.2

CELL REACNON

ln either case of these two cells as described above, as the ions move over a finite distance (greaterthan interatomic distance) electric current has to flow and thus the electrical circuit needs to be completed. This is posible in both these cases as shown in Fig 13.11.

ELECTRON'C CONDUCTOR

ELECTRODES

Fig. 13.1 - Galvanic cell showing

)
ru

z
J F

the ion and electron flows.

I
ELEcrnoLYrts

l!

oR

BRtDGe

yEssEt

The electrode reaction as in Eq.(13.'1) is an anodic dissolution reaction or is known as anode-half-cell reaction generating electrons which are transfened through the electronic conductor to the other electrode where the reaction

Nn*

+ ne

(13.3)

takes place resutting in deposition of N on the cathode or it is the cathode-half-cell reaction which consunes electrons generated at the anode by the anode-half-cell reaction. The overall cell reaction therefore shall be

M+Nn* + M*+ N

(13.4)

There is a conrention of describing a electrochemical cell. The Daniel Cellcan be represented

zn I znso+ t*rt ll cusoo (sol I cu

(-

ve)

(+ ve)

in sucfr a way that positive charge mo\,es from left

to right

(anode) and right hand electrode is positive (cathode). The vertcal lines in the above represenl the phase boundaries. The cellreaction is as shown in Eq.(13.2) and which is a natural process. lt only means that Zn is at higher chemical potentialthan Cu or CuSO+ is at higher chenrjcal potential than ZnSOa and hence the above reaction is naturally possible. Cosequenily the cell shows electro-motive-force, emf tor short, across the two electrodes. The concentration cell can tlren be described as

i.e. left hand electrode is negative

zn I znso+

where concentration Cr < concentration G z. The natural process is that the higher concentration (Cz) solution will decrease and the lo,rrer concentration Cr shall increase and accordingly the current shall flovrr. ln this case by dissolving Zn on the left hand side the Cr concentration of ZnSOa shall increase and by precipitating Zn out of ZnSOa from solution of
concentration Cz shall decrease.
145

1Cr)

tsor)

ll znsoo 1"orr I Zn
1Cz)

external enrf is superimposed on the cell to counteract the cell ernf then a stage can reach when the superimposed ernf exactly matches the cell ernf in the opposite direction, when no current shallflou in the cell circuit. There will be no net reaction of migration of ions or electrons. This is the equilibrium state and all thermodynanic considerations of the cell, since at equilibrium of under reversibld condition, can be applied to such a cell system with no net current floru' Example 13.1 : The electrode potentials for is - 1.82 volts co*2 + Co*3+e is - 0.15 volts. + + 2e Sn*4 andfor Sn*2 establish the cell that will be useful as a Also Which one of these two will reduce the other?

lf

source of ernf. Answer : Subtract the haff cell or electrode-reaction

of

colbalt from that of tin. lt gives

Sn*2+2co*3=2iir-*2+Sn*4
the cell ernf would be the algebric sum of these two
t.e.

- 0.15 - (-1.82) = + 1'67 section the free energy change of such a electrocemical prosses is next in as will be shown AG=-nEF=2x 123061 x 11'67 = -77023 cal/ g mole
emf =
(wherein the value

of r tras been used as 23061 cal/v/g.equivabnt)

This is thus a feasible process and hence Sn2* shall reduce Cos* or reaction of tin shall reduce reaction of cobalt. The cell therefore rnay be constructed as :
and that this wherein the positively charged ions shall move from ldft to right as is required cell shall have net ernf as 1'67 tlolts."

inertmetd

lSn*z lSn*4

ions

ll Co.s ions lCo*2

linertmetal

13.3

INTERCONVERSION OF FREE ENERGYAND ELECTRICALWORK Now

G=H_TS =U+PV-TS
66 = dU + PdV + VdP * TdS SdT

On difierentiation

where according to first law

and substituting in this the second law statement giws

dU=g-PdY-Aw'

6q = VdP - SdT - 3w' therefore 0and when the cell works in open'normal atnnsphere at room temperature dp = 0anddt= (13.5) dG = dw' therefore potential to one from charge electrical i.e. The electrical work done by the passage of current another over a potential difference w' = charge x potential difference(vottage) one gram electron As per Farraday's Laws for cell reaction when one gram atom is deposited, is denoted bY 'r" or 96500 coulombs of charge flcnrs through, This is called Farraday and electrical work Ttre number of electrons involved in a cell reaction, if n, then nf is the total
146

69 = TdS - PdV - 0w'

done by the cell through the cellraction and if the cellvoltage or ernf is z then the work done
or free energy change (13.6) LG = - rYEf for one mole is lf dn is the number moles of the ions passing through the cell for a spontan+ous celi reaction then

AG=-ftEfdn
Now since AGo is the standard free energy change then conesponding
EO

(13.4

would be
(13.8)

therefore substituting

- tEof in AG - AGo = - RT ln K as in Eq. -JYET * nEfo = -RT ln K

AG =

(7.8)

E=Eo * 4 hK

(13.e)

The sarne relationship can be defined by considering a general reaction as in evolving the equilibrium constant wherein as in Eq (7.6).

^c-^co
tur

Rr'"**
(13.10)

rvEo

fo = RT ," "9 + aR aB
RTln' a8 a$
aft
aB

where f, o is the cell enrf when reactants and products are in there standard states and then AGo = nao f
Thus

f,,=Eo+
ACTIVITIES AND EMF

(13.11)

or
13.4

= Ea + RTInK

as in Eq. (13.9)

Nornrally it is not possible to have a cell reaction in which sewral reactants and products will be constituting the cell reaction. These are vgry limited, often to one each and
therefore

E = Eo + RT 1n O reactants

?Product

(13.12)

This is also valid at only reasonable concentration and not at too loyv a concentration of either the product or reactant, otheruise r might tend to becorne infinite. The concentration cell is therefore simple enough to analyse. lt can be represented Pure metal A electrolyte
with An* ions

inpure metal A
i.e, alloy

The cell reaction in this case is

A (prre) +
AG = AGo

6mpuc or a!oy)

RT

ln

an timPul.e)
aA (pure)

(13.13)

'147

aA (pure) is one and when both are pure electrodes the cell enrf is zero and hence AGo

=0

and it will reduce the above to

or log an = ## AG = RT ln as = - nAz- f which is extensively used for estinration of activities of various molten alloys using emf
measurements. Also activities of compounds us take cell as

in solution can also

be found from galvanic cells. Let

Wwire

lng lAgzO.BzOe.Sioz l02

4 (Ag) + {Oz} = (2Agz O)r
E1 = Eo
E1

(latrnosprerel

Ptwire

The net cell reaction is

(electo}yb rnelt)

+ #

ln

a2

similady at some other concentration of (Agz O)

the enrf can be measured as

_,-2=

out of these (Agz O)z can be taken as pure or melt saturated with Ag zO and therefore the (Agz O)z shall be one and subsequently the activity of Ag zO at other concentration can be found out. This technique in principle is used extensively for estimation of activities of oxide components in molten oxide systens of interest in extractive metallurgy and in refractory
materials. Example 13.2

#," ffie)

Forthe cell

oz (r 'tno") pt Bzog sioz (silica sat. melt) the cell ernf was 1 .70 volts with Ag-Si was saturated with silicon. The cell emf was 1 .55 vohs when Nis = 0.1 in the Ag-Si alloy at 11150o C. Also calculate the standard free energy of formation of silica at 1100o C and acivity coefficient of silicon at N5; = 0.1 Sblution : The cell reaction is Si + Oz = SiOz where all are in their standard
[,to

I ng--si I

states.Therefore

AGo

= -n|r - 4
[Si]

x fl.ZO

123061

= -156814cailg

mole

(wherein lhe vdrc When silicon is not at unit activity then the cell reaction can be written as

of Fanaday constant is 23061 calfu/g equiv)

{O2} = <SiOz> K = l ( SiOz> / alsq x p{or} and since the'activiV of silica is unity and because the electrolyte is saturated with silica and since oxygen is at one Stmosphere

"

therefore Hence or or or

K=

1/atsil

AIso the non-standard free energy of formatip.q-of silica is

AG=-IrEf = 4x t{j.5*flx 123061 = AG = AGo + FIT ln K -142978 = -156814 + RT'n =L alsil Rf ln ! = '142978 + 156814
a[si]

-142978

log

a1si1

2.11 i.e

a1si1

0.007

1zA

or
Example 13.3
if the cell emf

ysi =alsil/Nsi =fffl=0.07

:
Calculate the {ree energy change at 8000

C for the reaction

FeO+Ni = NiO+
cell

Fe,

for the

uo I uooz I electrolyte I r"o I r" and for cell Mo I UoO, I electrolyte I f.fiO I rui
Solution

is 17,8 mV

is 28.4 mV both +r 800oC.

is

Cell reaction

of

tuo I naooz I electrolyte I f"O Mo + 2FeO = MoOz + ?Fe

I r"

and for which the free energy change is, assuming FeO in pure form

a G% =
and for the

t ."fu - n Ef = -RT ln "rt'root lMo x aF.O

cell n,lo I n,loo I electrolyte I ruiO I Ni Mo + 2NiO = MoOz + 2Ni cellreaction is ,.=fr' lGffri = - nEr = - RT In 9U9o'and aMo x aNiO For the reaction FeO + Ni = NiO + Fe the free energy change lGPe-r.ri = - RT rn *9# aNi x lFeo
Dividing AGFe-Ni

Therefore
13.5

/ AcRr, = 2ln +9:= aNi x ?Feo 4x 28.4x F 17 '8 aGo = - RT ln 28.4 cailg mole. 650 ==
AGPe

17'8

TEMPERATURE COEFFICIENT OF CELL EMF

Nowsince

/j4 G\
and at constant Pressure

nEf dAG = - n f dE
AG =

=-nr t-ait;

dE

(#),=-^s
and since cells are generally operated

at atmospheric pressure this condition holds true.

Therefore AS= ^t#

It means that the r values are to be measured at various temperatures of the cell and the slopeof the plotof c vs. T givesthe entropy changeforthis reaction. Once AS is known from knowledge of measurement of r vs. T, AH can be computed as

AH=AG+

TAS

--n?-y+nrT:f
'149

Once AG, AH, and AS are known along with the activities of the constituent of the electrode then by using the following

6X =RTlnan = -nA E f

s[ = nn'(#),
HX = na r E tE

-r l#) l.dr io'

and exeess properties can also be calculated.

is 1.2 vohs Exampte 13"4 : The enrf otthe cell co I coctz -Cuglz I cu at 0o d and 1.15 volts at 25o C. Calculate the AH of the cell reaction at 25o O. Solution :'The anode reaction is Cd + CA*z + 2e Cu*Z+ 2e + Cu and the cathode reaction is The fiee energy change of the cell reaction is

nnd

values Now since

- 2 x 1'2 x 23061 = -55346 1.15x 23061 =-53040 AGzgsok =-2x 4%=#@ and after puttins the abor,e AS = # =
AGzzsok

AH= AG-TAS
= -, 53040 - 298

g2.2caVg mole/0o

(-92'2\

= -25624caVg.mole
.!3"6 SOLID ELECTROLYTE CELLS
ThOz-aO' thern by coniCuction of ions. Some typical examples are ZtO -CaO(4%), a certain above conductors as ionic Thoz-yz os (7"a1 or ThQtanthana. These behar,e o oxide are these o{ygen partial pressure which is fairly,lol like 1 0-1 atms at 1 0000 C. Since can be and cells made with special oxides as electrolytes at high temperatures, these
reactions at various have been used for thermodynamic measurements of oxidation reduction pressures of oxygen including vacuum' The cell used are of the tYPes :<

through Certain solid solutions behare as ionic solutions since the current is carried

cD - < crz Qg> I zro, < cD - < crs 03> I z,o" -

cao) I fot in Fe alloy (7Y"Yz os) | tq in Fe alloy

(a%

for which the cell reaction is

or

2t <CrzOe> ! <c> + [O] = - E E - E" = # ln ao since bith Cr and Crz Os are in

solid state.

150

Where

in Fe is replaced by orygen is calculated fiom the measurements of cellwhen [O] knowingthefree energy of formation of at one atmospheric pressure or can be.calculated has been reduced to < Crz Oe> taking c as 23061 cayv' This 13580 --10'oB E log ao = 4'62 -

ro

K where c is expressed in rnilirlolts and T in C, P, Mn, S etc' like in Fe with any other elernent By employing the right hand electrode as [O] can also be found out' The results'haw and thus even the interaction parameters tally with actual rneasured ones in most cases' extreamly good in that the calculated ones A cell of the tYPe the log {io

= eL t z' i)

been

<Mo>
if set uP, means

I tMoo" lz'ot-c"o I
+
RT
afri ln luoo'

truio'<Nio>

s, = Eo

aNio'aMo

EnE

ChemicalpotentialofNi_Nio-ChemicalPotentialofMo.Mooz

Knowingchemicalpotentiall.e.partialmolarfree:n"'qlofoneoxidetheothercan befoundoutbymeasuringthecellen/-x,.oralternativelycellenrfrisrelatedtothefree minus sum of the free energies of products energy of cell reaction anJwhich is the algebric

oxide' can be found out knowing AG of the other reactants and f rom these the aG of one oxide

13.7

CONCLUDINGREMARKS

For example the conductance measureElectrochemical measurments are rnany. is on. But the electrochemical process or the change' ments, ion transport estimation and so system' by the passage of current through the only the change in chemistry accompanied with this process and hence is of direct The energy exchange is inalienably associated

interestinthermodynamicmeasurments'Thetechniqueoferrrfmeasurmenthas.been the of thermodynamic parameters' in particular extensively exploited ior the estimation properties of the system in which the chemical activities and therefiom the other energy The use of solid electrolytes has the form of electrochemical'processes.
reactions occur in at fairly high temperatures' opened up a large vista for measuremenis

151

CHAPTER

\4

FREE ENERGY- TEM PERATU RE RELATIONSHIPS

ellingham d.iagrams
14.1 tNlRODUCll0N
The free energy composition relationships were discussed in Chapter 12 to confirm nature of phase equilibria inwlved in phase diagrams. Often it is necessary to know the the free energy-temperature relationships, which are nothing but equilibria as affected by temperature, to establish the temperature at which it is advisable to earry out a certain process, particularly the chemical processess. Free energy change in a process is an indication of whether the process is at equilibrium, or it is natural or spontaneouly occurring or, it is an unnatural process. Since most processe of interest are as such unnatural processes (see Section 1.1). the conditions, particulady the temperature is of direct interest for its commercial exploitation. Free energytemperature-pressure relationships are of direct use in this regard. Any material form, say for example iron oxide, as sorne oxide mineral of iron, needs to be reduced to produce iron. lron oxide as such has a fairly loru value of free energy and hence stable. Had it not been so iron would have been produced as a natural process, which is not the case. Conditions can be altered suitably such that iron oxide becomes unstable as compared to something else. For doing this pure iron oxide system is transformed into an iron oxide plus carbon system and heated to a.suitable temperature (above 9000 C).Thefree energy ofthismixtureishigherthanthatof ironandwhatewrother products,

CO or CO2 produced at the higfr temperature. The system therefore undergoes a transformation and produces iron as desired. lt neans the reaction
(14.1) FezOs + 3C = 2Fe + 3CO takesplace and the reduction is possible to produce iron.Knowledgeoffreeenergy-ternperature relationships is guidance to convert otherwise stable system into a unstable one and get the desired results. ln the reaction above, original iron oxide is destroyed, and a different one, oxide of carbon isproduced.Thecondition oftemperature,inparticular,isfixedinsuch a waythat the above reaction is possible or net free energy change is negative for the owrall reaction. The above reaction consists of two reaction equilibria as

ZFe+3l2Oz

FezOe

(14.21

which are, manipulated suitably for reaction in Eq. (14.1)to occour. With reference to above it can be said that if the relative stabilities of oides, as

2C+Oz

=zCO

(14.3)

to carry out they vary with temperature, are known a suitable pair can be worked out as above associated the desired process. The qualitative term stability is quantified as free energy oxide the the of formation with these various ofdes. More negative is the free energy of more stable is the oxide.

The same arguments can be made for any group of substances like sulphides' be destroyed to sulphates, chlorides, silicates and so on, in which case one sulphide will
produce another sulphide and thelike. lt means for example, that (14.4\ Sbz Ss + 3Fe = 2Sb + 3FeS of iron sulphide would be possible to produce antimony provided the free energy of formation the reaction at which temperature some at is more negative than that for antimony sulphide

will have to carried out' All chemical processes are qssentially making, breaking or both of chemical bonds. ones are formed' ln the manufacturing processes chemical compounds are broken and new the Being non- nuclear, the element remains the same before and after reaction but compounds change from reactants to products'

The free energy ol compounds i.e. free energy of formation of compounds can act as a stability scale for compounds and since free energy is a function of temperature energy of formation the stability shall also be subject to temperature as a variable. The free Eq.(14'1) is readily as in reaction hence and of GO is more negative than that for iron oxide
possible.similar is the story of reaction in Eq' (14'4)'
with The free energy value changes with associated interacting substances i'e' the activity of the constituents in reactants and products as

G=Go + RTInK
where
Hence the

pure to impure form of reactants and products are going to affect the free energy and hereby the relative stabilities. quantitatively examined in the following in terms of free

proAuct of activitY of reactants

changeo*ifro*

All these tactors are

energy-temperature relationship.

typically represented by reactions involving condensed phases' These reactions can be

I4.2FREEENERGYoFREACTIoNSINVoLVINGoNLYGASES difference {rom those This group is separately classified because of its characteristic

ZHz+ Oz=2HzQ 2CO +.62 = ZCOz

2SOz +'Oz = 2SOe Let us consider the free energy of reaction (14'5) AG = 2GHzo - ZGnz - Goz
153

(14.5) (14.6)

(14.4

This will be in equilibrium

Therefore Putting
where
the reaction.

2Gffro

if AG = O 2Gs.o = 2GHz * Goz as in Eq.(4.56) Gi = GP + RT ln pi 2RT ln pH2o = 2GPr, + 2RT ln pxz + G8, + RT ln

po2

(14.8)

pHzo, pH and po2 are corresponding partialpressures of the components involved in

Since

a G&a.st = zGR"o - 2G,ha - GBn therefore, AGlrc.s) = 2RT ln Pxz+ RT ln ps, + 2RT ln

pHeo

(14.9)

=
or

ZRr,^

= _ 2RT ln l$

#
l$ = ;ffi
rao
(14.10)

2los

where Kp is the equilibrium constant of the reaction when gases alone are involved. lt is different from the equilibrium cbnstant Kx which takes into account condensed phases as
discussed in Sec 7,2. For Reaction (1a,5) it has been estimated

aGfra.si =
therefore

at

118000

26.757

16000 C or 18730 K

2togKp,,ou,=

or

ffi
=
Poz

*
9.808

ffi
atmos

* 19.616

log Ke

lf it is assumed that the atmosphere required should have

= 10{
e.aoo

then
or

los Ke

**#
x
102

Pn'
PHao

9.808

= 980

lf pH, is one atnnsphere then PHzo = 1/980 = say approirrately 1 mrn Hg The temperature of water when its water Vapour has a pressure of 1 rnm Hg and if hydrogen gas is bubbled through the water at this temperature then the resultinrg gas mixture shall hare a ratio of px. /pn2o as desired above to be equivalent to partial pressure of orygen equalto 10a atmosphere. Similarly for reaction (14.6)

AGo= -115200+ 41.507

2logKe=+;#-#
al1273o or
2log Ke = 19.78 log Ke = 14.42
tog

9.071

28'85

Ke

ffi

p'$, -- l+.+z

lf partial pressure of oxygen is to be kept

at

Poz

1A-2

atmos"

154

The CO and COz gases will have to be mixed in such a way as to obtain the aborc ratio to obtain poz = 10-2 atmos. lt neans 142 ml of CO will haw to mixed with 1 nrl of COz to get the required mi)*ure. Often Co2 is generated and passed over carbon at appropriate temperature when COz + C = 2CO reaction shall qccur and the appropriate ratio of CO/COz willbe obtained. The details shall be discussed later' It is thus clear that if the sum total of powers to which each of the reactants and products are to be raised are equal the equilibrium shall be independent of pressure but if these two are'not equal, which shall often be the case, these equilibria inwlving onty gaseous components shall be dependent on pressure. The system shall then be defined at a given temperature and pressure and in that case at quilibrium the free energy change

Pco = 14.42 x 110 atmos. or PCOz

Pco
PCOz

142

willbe zero. These reactions are often between

elemental component gases giving rise to a gaseous compound and often shall be pressure dependent, A reaction of the type

two

CO+HeO=COz+
can be imagined and since

Hz

(14.11)

pco x pH2o appears as pressure independent. A clqse scrutiny of such a reaction shall reveal that this reaction is a combination of reactions in Eqs. (14.5) and (14.6). lt only means that the two
shall be independently in equilibrium at'a fixed po, value. For the Eq.
(1 a.

*' _

PCOex

PHz

1) to be in equilibrium,

p6rforbothofthereactionsinEqs(14.5)and(14.6)shallhave to be equal. lnotherwords the pressure is fixed for the equilibrium and that is what the K for (14.11) reveals.
1

4.2.1 Orygen

Potentia l-Tem perature Relations hips

Eq. (1a.5) gives

AGo=-RrrnKp=

Rrh[#5" q

(14.12\
(14.13)

or

= aco - 2RT ln fj}) \Pxzo,1 Forthe reaction (14.5) AGo = - 118000 + 26'75T caVmole Therefore RTrn poz = - 118000 + zl.rs r - 2RT f*31 '" \PH,o/
RT ln poz

(1a.13a)

For any fixed ratio of HpJHzO the RTln po2 can be correlated with temperature and it shall be a straight line. fhe intercept of this line on y-axis Le. RT ln poz axis shall be 118000 cal. This is shown in Fig.l4.1 in the form of point'H', When Hz lHz O ratio is one

the RTln

po. shall increase (move

in less negative direction because of

+ 26'75 T

factor)

'H' as with temperature and hence the line is sloping upwards from the anchor point temperature rises. lf Hzl1z 0 ratio increases beyond one, for ewry ratio the line will slope further up but originating from 'H'. lt Hz lHz O is less than one the term 2RT ln (pn. /pHro point lshall be + r,e and hence the RT ln po, will move to rnore -\,e side but every time the
155

RATIO

lhttko

rt. .6*rd dtc tr

rp
t;c
x;5 to I
r.d
-l

c
(il
<t

F E

d 5-:

lo

50

tp

2t

+TElrPcK

500

1000
los9

to4

Fig. 14.1 - Vari"att)n of RT in po, of the reactinn shall remain the same

2H + Oz = 2HzO with

temperature.

for all such relationships and hence all lines for various Hzl4ze ratios shall originate from point 'H'. For all RT ln po. has the same value as shown by point H. As HzlHzO ratio decreases below one the lines shall rotate in clockwise and when it increases beyond one in anti-clockwise direction as shown in Fig 14,1 .
Additional scale of Hz/HzO ratio is superimposed on this diagram in the form of additional y-axis.ln order to make the diagram a compact one since lhe y-axisextends on either side of x-axis over a long range ,the y-axis of HzlHzO ratio is bent at right angles and made parallel with x-axis. The lines emanating from the point H upto the vertical y-axis shall cut across the bent y-axis and which is now marked by corresponding values of the gas ratio ol HzlHzO. This obviates the need to have long y-axis and thereby the diagram becomes more compact.
For the reaction in Eq. (14.6) the free energy change

AGo =

This can be processed as was done in the case of reaction (14.5) to get

135000

41.S7Tcallmole.

hff) for fixed values of and by the same logic RT ln p6, can be plotted against tempbratuie
COICOz ratios as shown in Fig.14.2.

Rr rn po. = -

135000

41 57

r-

Rr ,"

(14.15)

The valueof RTlnpo2 at zero degree absolute is-135000ca| andisshownas

point'C'. Allthe lines forvarious CO/COz ratios shall originate from point 'C' and shall move
156

-t -l+ -!l to to to

.b lo

lo

-t
lo

{ { L'
c

tplo

t&

io
10

,o

t'tl
l+

#
to't
TEMP oK-5OO

lroo

t9

IEL

Fig.l42.VariationofRTlnpo,ofthereaction2Co+oz=2Cozwithtemperatute. clockwise on decreasing the ratio belorr one and anti- clockwise beyond ratio one on
increasing the CO/COz ratio. ln this diagram the additional y-axis is shown in the same way as in Fig'14'1' likewise. Sirnilarly for a reaction

is of CO/COz ratio and

This is the standardised treatment and may apply to even reactions in Eq' (1a.7) ZHz

the RT ln p9, shall now be replaced by RT ln ps, and related to temperature at fixed ratios of Hz /HzS. This is useful for sulphidation reactions. Erren a reaction of the type

32

2HzS

ZHz+Cl2=1116S
could be amenable for chlorination procasses as a function of ternperature and Hz/HCl ratios' So far,theratios ot{zlHz0, CO/COzand thelike areused towork outtheirvariation as a function of temperature and a function RT ln po, . The requirement is however to know the variation of RT ln poz 6 such as a function of temperature and partial prqssure of oxygen
itself.

This could be established using the relation given in Eq'(a'56) as

'

G=Go+RTlnp
it to
be the standard state for oxygen

then

lf

pi is one atmosphere of pure oxygen and assuming

confirming that it is the standard state and in equilibrium with one atmasphere of o{ygen' which is obVous enough. The RT ln po2 = 0 shall be the correlation of RT ln po, with
157

Go

tenperature at po, = 1 as shown in Fig 14.3 in the form of the horizontal line passing through the point RT ln poa = 0 at any temperature.

ta

lo'

to^
!o
-2 10

-t lo

Fig. 143 - Variatian of RT lf the gas is now at

ln P orwith

temperature

for various pressures of orygen.

then,

or in another words it will be the free energy

to a new state when po.

a pressure less or more than one atnnsphere RT ln Poe'= G - Go

change from standard state when

r 1, i.e. for the reaction (one dtnns) = o)rygen (other than one atnns) Oxygen This free energy change varies with temperature for a fixed partial pressure of oxygen as can be seen in Fig. 14.3. All these lines shall origanate from RT ln po. = O at T= OoK shown as point'O'in Fig. 14.3. lf oxygen pressureis less than one atnns (por<1)the lines shall moveintowardsmore-ve freeenergy and if olygen pressureis
more than one atmos (port t1 towards + ve free energy values. This is obvious because pure oxygen, being at higher qhemical potential shall change to oxygen at le-ss than one atnnsphere as a natural process or spontaneous change with -ve free energy change and just the opposite when pe2 1 atmos. 1s8

p9, =

As before an additional y-axisaspg, is provided on the diagram as shown in Fi9.14.3 equilibrium of reactions as in Eqs. (14.5) and (14.6) indicate that at a fixec

The

ternperatureif theCO/COz and the system is invarient.

sr HzlHzOratio isfixedthenRTlnpoz i'e'poz assuchisfixec

clear from the expressed in different forms for a certain fixed temperature. This will be folloriing. LetusdrawafallinesofdifferentCQlCOzratiosoriginating frompointCanddifferenl Fig.l5'4- Lel: lines originating from point O such that they intersect each other as shown in
P%

ln fact therefore co/coz , HzlHz 0 and po2 are one and the same thing

u
o

.{.
U.
d

TE,{P

oK

5oO

Fig.l4.4.Theinterrelationshipsofpo,,ColCozandHiJHzoratios

und the method of determining these graphically'

the above mentioned intersectiort us draw a line originating from point H and passing through

point A as T as shown' Therefo'tr also work out the temperature corresponding to this ratio to be read from relevantl at temperature T the point A indicates certain fixed CO/COz
y-axis. direction o-Ato lxr The same point A also indicate a certain fixed value of p in the read from aPProPriate Y- axis. equilibritrr lf alineisdrarynfrom H through point A it will read thecorresponding H/H1O ratio on the conesponding y-axis'
159

Let us say that Poz and

co/coz lines intersect at

a point shown

as A' Let

tri'

Therefore at the temperature T in Fig.14.4,

CO/COz ratioof 10-2 = po, of

104 = HzlHzO

ratioof 10-1'2

ln otherwords the orygen potentialcan also be depicted at any temperature by eorresponding ratio of CO/COz ar HzlHz O. So for a certain po, value at a certain temperature the equilibrium CO/CQ ratio can be found out like this. Draw the relevant po. line originating from the point O. Draw a

vertical through the required temperature to intersect this line. Draw a line from point 'C' through this intersection to read on COICQz ratio axis. The value obtained is required COICQz ratio. lf in stead of through C, line is drawn through point H it will read the HelHzO ratio on the HzlHzO axis in equilibrium with poz . This is shown in Fig.14.4 by the point B at temperature of 9000 k when poz of 10{0 = COICOz ratio of 10-12 = Hz l1z O ratio of 1011. lt

O ratios for a given partial pressure of o4ygen. All these indicate the oxygen potential of the system in various forms.
is rather easier to obtain the equivalent CO/COz or Hz l{z
FREE ENERGY OF REACTIONS INVOLVING ONLY CONDENSED PHASES

14.3

This is other e>trerne when

Such reactions can be exemplified as

no gaseous component is involved

in the process. (14.12)

(14.13) or e\n carbide forming reactions from carbon and metal also falls in this category; and such

+ SiOz = 2CaO. SiOz Ale Oo + 2CaO = 2Ca0. Alz Og

2CaO

others which are more common in ceramic systems. The reactions of this type are possible only because the two condensed phases harre opposite chemical characters.
Reactions of the type

CaO

MgO

solid or liquid solution

leads to solid or liquid solution and not any chemical compound . Out of the simple compound types therefore acidic oxides like SiOz, PzOs and sornetimes Ala Oe form chemical cornpounds with alkali or alkaline earth metal ofdes as silicates, phosphate and aluminates. The fiee energy change of these reactions are independent of pressures. These

however do change with temperature, as it should be. The free energy is given by

AGo= aHo-TASo
in which the enthalpy can be treated as substantially constant and is equal to the intercept of

the line G vs.T on the G axis at zero degree absolute. The entropy change in the type (14.12) shall be

a reaction of

AStt+.rzl

S!c"o.sio.

Slc,ro

SBio,

Since all are condensed phases the individual entropy values are small and are often of the sanre magnitude'for many substances in the same physical state. Therefore ASo is very smallfor such reactions. The net result is that the AGo vs T plot for such reactions

donotvarymuch with temperatureand hence areparalleltothetemperatureaxisas shown in Fig. 14.5. These lines do change their slopes if the reactants or products are not in their standardstates.This non-standard behaviour shall bediscussedinageneralisedway later. These plots also change their slope when phase change occurs in either the reactants or the products or both. This also will be discussed in a generalised way for all reactions later.
160

o
o

f
!

d (,

TEMPEMTURE+
e r a tilre re latio ns hip s of reactians involving only condensed phases.

ro00

F ig. I

- F re e e nerg) - temp

14.4 FREE ENERGY OF REACTIONS INVOLVING

PHASES

CONDENSED AND GASEOUS

nent like oxygen, sulphur, halide, carbon dioxide, carbon monoxide, and so on. ln fact in the inorganic world these reagents dominate and hence becorne a part of processes for
consideration. The free energies

what will be the differance if condensed and gaseous components are involved in reaction ? There is considerable difference between the earlier two categories and this category as far as the free energy of reactions are concerned. By far this is the most widely encountered practical system, because chemical changes often involve a gaseous compo-

of the type:

of reactions involving any one of these shall be a function of pressire of such gaseous components. The free energy does vary with the purity of the condensed phase (s) in the reaction but this deviation shall be discussed later. lntially only pure condensed phases shall be deatt with, The equilibria is typically described by realtions

or

MetalM +egas=Meoxide Metal M + Sz Gas = MSz sulphide and so on.

Let us lssurne that the temperature for consideration to be belor the metting point of both metal as well as the oxide and hence let us study the heterogenous reaction of interest exemplffied as

M (solid) + Oe (gas)

MOz (sotid)
161

(14.14)

or as per the conrention used

<M>

+ {O2} =

<MOz>

(14.141

The temperatures are such that the partial pressures of M and MQ in gas phase shall be extremely small and each oi this solid phase shall be in equilibrium with its o\ rn vapour pressure. The free energy of solid phase is thus equal to the corresponding partial part in the gase phase. Under the present conditions the partial pressure of solids in a gas phase vary negligibly eren when pressure changes considerably. Hence the free energy of solid phase can be conwniently assumed to be independant of pressure and thereby assumed to be constant.The gas phase equilibrium can be written in the form of reaction as in Eq. (14.14) and the solid statqs thernselves to be taken as standard states.
The fiee energy change of reaction (14.14)

is thus

AGftr.rl;

AGftoz

- AGRr. - AGU
(14.15)
I

and

I =-Rrrnlila aM x po2l

AGo =

RT tn

k = + ni

ln 1ps,1

(14.16)

where K is the equilibrium constant of the reaction. It also means that free energy can be expressed in terms of partial pressure o{ orygen as

AGo = RT ln po,

and therefore the y-axis plotted in Fig. (14.1), (14.2) and (14.3) as RT ln pe. is nothing but the standard free energy change AGo of the reaction. Thus the RTln poz w.temperature plots for metaUmetal oxide systems are nothing. but the free energyltenperature relationships. Likewise the RT ln ps, shall be the free energy term for sulphides in such diagrams.

fi4in

TheAGft+.r+listhusthestandardfreeenergychangeofthereactionasin Eq.(1a.1a). Since K is a function of temperature, at any fixed temperature the equilibrium shall be decided by the unique value of the partial pressure of o4ygen in contact with solid metal and its oxide. From phase rule it can also be deduced that the equilibrium in reaction (14.14) has only one degree of freedorn.
Therefore in a metal-metal oxide-oxygen system if partial pressure of orygen is less than the equilibrium value, metal oxide will spontdneously reduce to make up the partial pressure of oxygen to the equilibrium value and if the oxygen partial pressure is more than the equilibrium, the excess oxygen will spontaneously react with metal to reduce itself to

theequilibriumvalue. Both solid phases, of course, must existtogetherforthistohappen.

The actual value of equilibrium p9, depends on the temperature and if the ternperature varies itsvalue atsovaries accordingly. Similartype of equilibrium partial pressures of sulphur

in the case of sulphides, of COainthecaseofcarbonates,ofHzOinthecaseofhydroxides, of Glz in the case of chlorides and so on shall be existing and could be erraluated, ln all such equilibria therefore, if equilibrium partial pressure of orygen (in oxide reaction) and the others in the conesponding reaciions, if plotted as it varies with tenperature then the equilibrium gas pressure line shall divide the area in such a way that the conpound plns the gas shall eist on one side and the metal ph.s gas shall exist on the other side as shorn in Flg.l4.6.
162

o
ZnO
02

tr

or-40

crl o

A2

INVERSE TEMPE RATURE

o'5

1'O

t'ta*"ot,

2.4

Fig. 14.6 - The varintian of equilibrimt arygen potential with temperature orygerL for a system containing zirc and. oxygen and" zinc oxi.de and

14.4.1 Varlatlon of Free Energy wlth Temperature The free energy change in a process is given

by

change It means that there nny be a change in enthapy and entropy of the system leading to nd being in free energy of the system. Although AH varies with tenperature, the variation large, it can be treated as substantialty constant o\r a hirty wide range of tenperature

AG= AH-TAS

pfo@ss' without inwlr,ing much enor. The As horever changes with tenperature in a phases' condensed with the along partiorlarlywhen ga.seous phase is inwfued ln the generalised chemical process of oxidation of an elernent as depicted in the enthaply Eg.(14.14), if the reaction occurs as a natural process, may be after initiation, in gOs disappears change of this proess shallbe negative. Since one g . mole of o4ygen this process the entropy must decrease appreciably in this process. conditims. TSese changes are qualitatively shown in Fig. 15.7 plotted under standard entropy the and The plotting of such a plot needs the knowledge of enthalpy of this reaction ralue of change accompanylngine process. The slope of the AGo r,s. T plot is ASo . The calcualtions for taken are exanples - TAS; continuously increases with temperature. lf actual

all will slrorv simila'r and the AGo values forvarious oxide formation reactions are plotted, they originating from various lewls on the free energy axis equivalent to AHo of that

straight lines

reaction. For similar reactions of variotts oxides the entropy is given by (15'16) So(rrpu0 -. Sopxypnpcl possible 1n and since So 1O**1 and So (mcbD are practically the same, within the accuracy of such catculations, the entropy change arlse predomlnantly due to dlsappearance

ASo = Soloritc;

163

i+

tooo

Fig. 14.7 - The variation of free energl, enthalpy and entropy for the reaction with temperature' 413 <Cr> + {Oz} , = 213 <Crzos> (LGo = - 178500 + 41'4 T) callgmole
one g mole hence lt is negative. The entropy changes in various such value. The AGo vs'T metal oxidation processJs are expected to be substantially of the same fornrat of the plots therefore slope upwards, towards less negative values of AGo ' lf the ieactions change from that in Eg' (14.14) to something like:

of orygen gas and

(14'19) (14'20) or other' even intersect each their slope is likely to change and in that case thege lines may AGo vs'T plots in sorne of these of slopes There are exceptions to this general nature oxidation reactions. The case of
<

2M + Oz = 2MO 4lg Al + Oz - ?3 AlzOs

C> + {Oz} = lCOz}

(14.21\

gives entroPY change as

lSf+.ztl=S8oz-Sc-So,

since
be a

and Since the gas entropy values are far more than that for the condensed Phases Sc or soa sc Scoe Scoa

= 56, and

>

>

and therefore the resultant ASo

dioxide gas has to It only means that the AGo vs.T plot for the formation of carbon coz of nearly horizontal line as is the case. This is the exceptional behaviour

= O for the above reaction'

c*

reaction. ConverselY for a reaction

1g

2C+{O2}=2tCO} ASo=2Sco-2Sc-Soz
C

(14.221

the resutt is increase in entropy, as volurne is nearly doubled, for the same pressure. The slope of AG vs.T shall therefore be reverse of that of the earlier metal oxidation reaction.

This is in fact true. This

CO reaction and slope being in opposite direction, this line cuts across many other oxide lines and alters the relative stabilities of the oxides vis-a-vis the carbon monoxide line and which is fully exploited in extractiw metallurgy for metal extraction purposs"
is yet another exceptional behaviour of

14.4.2 Free Energy Change With Change of Phase. So far the discussion centered around when both the reactant and the product remained in soiid state. While probing the free energy temperature relationships the temperature of interest may be high enough such that either the reactant or the product or both melt or evaporate because the temperature under consideration transgresses their melting or boiling points. The question arises as to whether the straight line relationship of
free energy and temperature continue to be the sarne or change at these temperatures when phase changes occur? ln other words will it have the same slope or the slope changes? Let us take the case first when the metal or the reactant first melts. The reaction then shall be written as (14.22) (M)+{Oz}={MOz} shown as one value has all are solids when temperature upto the reaction the of entropy The as in Eq.(14.19) from that is different this reactlon of change entropy in Fig.14.4. Now the

AS[ra.zzl

= SMoe Su

So,

(14.231

lf the Eqs.(14.19) and (14.231are compared, earlier the entropies of solid metaland solid oxide were equated, but now being different phases, are not that similar to be equated

to canceleach otherand hence Srr,t (liq) > Su (sotia). ASo = more negative ttan when both were solid, Hence

and in that case if the free energy of Eqs.(14.19) and (14.23) are compared as

lG?= AHo-TAS? when reactant is liquid AG8 = AHo - T ASa wherein -TAS?<-TAS8
allsolid phases

-AG?>-AG2
ln otherwords the plot shallslope further upwards or slope of this AG vs. T relationship shallbe more as shown in Fig.l4.8 fromthe point of temperature as melting point. Since the entropy of melting of many metals has fairly the same value the plots for many metals may again be parallel originating from their respectiw melting points onwards.
lf the temperature of the process of oxidation

is such that the reactant boils, the value

be still morenegative than that for liquid. ln that case the AGo vs.T plot shall slope further upwards or rnore tcnrvards less negative value of AGo as shown in Fig'14.8. Let us now consider that instead of reactant melting, product oxide melts first then
of - TASo shall

the entropy change shall be

165

('
td

'Tat?) h(P)

z lll
ad

ul

t Ir

// ./ ,', Tr94--'
,'

Fig" 14.8 - Vari"atinn af free en' ergt with temPerature as Phase changes takz Place in reactnnts cndproducts.B is used to de-

og
rll

rnte boiling Point ntd

ttsed to

derwte

M is melting Pint
used

The
uct.

subsgriPt

R is

for

reactant and P is used for Prod-

I
TEMPE RATU RE

ASo=Sogqridoxiic) -So(solilmcbl ) - So{st")

(14.24l.

less negative than when both are solids more negative than when both are Therefore the free energy in this case shall be oe more negative than when mefting of the solids and as a result the slope of the line shali dowrnalards when it boils' The combination reactant occurs. Likewise these lines bend further The actual values for a oi allthese changes haw been shown Fig.1a.8 schematically' values of various phases involved in specific case can be evaluated knowing thl entropy

the reaction
Exanrple 14.1

For three difierent

forns of reactant metal M, solid, liquid and gas, being

oxidisedtoproducesolidmetaloxide,threedifferentvaluesoffreeenergychangeswere
obsened as

(1) 2<M> + {o2} = 2<MO>

M? should be oi formation of soia oxide from solid and liquid M Solution : The lree at temprature give the "n.tgy when equated shall same at the m.p. ln othei words the two AGo which AGo shall be zero. to obtain the required are three equation-pairs narnely t-2, t-3 and 2-3
specific state of How to know which on" of thepe is for which

tzl 2(M) + {Oti'= 2 <MO> (3) 2{M}+tbzi =2 <Mo>

AGo = AGo =

aGo=-298400+557

-290400 + 46 T - 3587s4 + 1027

Therefore there tenperatures'

1--3 2-3 1-2

when equated,

T = 12200 K When equated, gires T = 88Bo K when equated, gives T = 13050 K

gives
166

The question still remairs, ev,en if 1-3 are solid-liquidtransition, beingtheloresttransition tenprature, which one of the 1or 3 is for solid ? lt is clear that m.p must be 8880 K, and B.P 12znoKTheambigurtycanbesolvedbyevaluating values of AGo atanytemperaturebelow 88g Le. say8000K, in between 888and12200K i.e. tosayatl20ooKandabovetheb.p. 1220i.e. say at 12800 K.
The values are as follows: Temperature 800 reaction 253600
1

reaction 2

reaction 3

All reactions show negative free energy values of AGo and hence can be

1200 1280

correlated 3 at 8000 K land between that expect is logicalto lt 14.8(B). in Fig. shown as schematically line' dotted supercooled shown by as be liquid shall -ve value AGo whatewr shows lass ol proof gas. is thatAGo The is for 2 Obviously liquid. Hence Eq 1 is for solid and 3 is for case. reaction 2 at 12800 K must be least - ve and which is the The same can be argued in a different way as follows: The entropy change in each one of these three cases has to be relatively calculated
as

-2544ffi -231520

- 256754

-277154

-228194

-25440 - 24i1400
-288000

follors:

SFrygengas) - S(mctal) The entropy change therefore shall be in increasing order in the order

(1) WhensolidM ASo = S@xide) (2) WhenliquidM ASo = S(oxlie) ASo = S(oxae) (3) When gas M
solidM liquidM + gasM

Slo"vgengas)

S(oxvsengas) -

S1maary

S(rnbD

The entropy values are given in the three equatircns as a muttiplier of temperature T
Hence the equation of fiee energy lor reaction 1 is for solid, 3 is for liquid and 2 is for gas.

A-{ELLINcHAM

DIAGRAMs

These are the free energy vs. temperature relationships which were plotted fol various oxidation and sulphidation processes of several metals and gases by H'J.T.Elllngant during the second world war for the first time and these later became known after him asi Ellingham Dlagrams. Now such diagrans are available not just for oxides and sulphides bul: for many other cornpounds like chlorides, carbides, nitrides, carbonates, hydroxides and sci' on and also for many conplex compounds like silicates, sulphate, phosphates, and thelike

Ellingham diagrars for simpler compounds are by far rnore useful and hence moret popular. ln each one of this diagram the basic reaction is formation of the relevant compouncll from respective elements, one of which shall be the anionic part like oxygen, sulphur, chlorine,

The

and so on. These diagrams are konwn by these anionic part as 0xide'Elllngham-Diagrams',

Sulphide- Ellingham-Diagrams, and so on' lnitailly only oxide diagrams were prepared but soon the others were also plotta:il because of their importance. The diagram plotted by Ellingham for oxides was recast blr F.D. Richardson immediately after the world war second. lt includes not only the AGo Vs.'li' relationship but also superimposed on this diagram are the additional axs of prs, , CO/COru ratio, HalHzO ratio scales and relevant O, C and H points as shown in Figs' 14.1 , 14'2 ancll l4.3.lnotherwordstheFig 14.1,14.2,and 14.3 are superimposed ontheAGo vs.Tdiagramr
167

As the electrochemical series is scannd from noble to baser metals downwards, nearly similar order, though not exacdy matching the same is observed, as the lines ere scanned from top to bottom in this diagram. The nobler metals are at the top and slowly change downwards to less and less noble to traser ones towards the lower side. 6. since the - ve AGo moves downwards the rower is the rine the lower ie the free enerry of that oxide. In other words the lower oxides ere relatively more stabler than the ones above it. Obviously the nobler metal oxides, which are most unstabre, are at the top and the stsbler oxides of the baser metals are at the bottom. This relative stability is true et any given temperature. 7' The carbon'cerbon monoxide line on this diagram is exeeptional in thet it slopes in the direction just reverse to almost all other oxides. In other words the -AGo value for this reaction goes on increasing with temfoerature. For all other oxides, except carbon dioxide, the - aGo go on decreasing with temperature. The carbon-carbon monoxide line therefore cuts acroas many of these oxide lines and thereby reverse the relative stabilt5r relationships with the eorreslrcnding oxide after the intersection. 8. Any point on this diagram means certain temperature nnd certain ' value of AGo or RT In po, . rf this point is joined to either .o, or .c, or .r1 points on the graph and extrapolated, ean give the equilibrium partiatr presaure of oxygen or equilibrium ratios of CO/COz orlf,z/IflrzO in contact with metals and their oxides. Therefore such equilibrium parameters

temprature over the range shown in the diagram. The diagram currently in use and re'ferred universally is shown in Fig 14.9. The characteristics of this diagram are discussed in detail in the follorrving. These are : 1' Several metal'metal oxide systems of interest in chemical and metallurgical engineering are shown in this diagram. 2' The Zero free enerry trrcint is at the top and the y-axis is shown in the form of, -ve AGo values. 3. This is a standard diagram meaning thereby that the reactants (metars) end the products (oxides) are all in their standard statee or pure etates, i.e. et unit activities. 4' Alnost aII oxides have negative free energy of formation. The exceptions being the nobre metars like platinum, gord and to some extent silven

It also means that the present Ellingham diagram for oxides includes the free energy temperature relationships for various metals and provides means to obtain equillibrium Co/coz ratio and equilibrium HzlHzQ ratio in contact with metal-metal oxide system
at any

The free energy is shown on y-axis but as per Eq:(14.17) it is atso the sarne

n"

RT rn psr2

5.

168

o
20

1;;;;"
gie

to'
=C

4 6r +O1 z,2CryO
at

C+qt rCoz

a (,

v
.g

GI

Lzs

L4o
L6o

fuofU

F t
tl

oct
I

tfo

2'20

tot

24
%o

N.?, g.P.
-27'
d

t'1.?.

ELEME{r EtgME{T
Q.,DE

ook

2o,o' 4@ 5@ T5fiP-..+ oC CAtCo2

Coo

looo
Poz.1

leoo illo0 leoo igoo

llr/HrO
Fig. 149 - Ellingham diagramfor oxide systems.

169

g.

10.

any temperature for any oxide csn be found out by ssaascfing the point to the pivota 'O', 'C'or'H' as per requirements. This has alreadybeen discuseed in Sec. Q,4.2.1\ and Fig. 14.4. The lines on the diagram for most metals are nearly parallel as discussed in sc. 14.4.1. The slope of an individual line may alter on pslt'iang or boiling of the reactant or product or solid etate phase changes therein ea discussed in Section !5.4.2. This therefore may result in intersetion of aome lines snd thereby alter their relstive stabilities' Free energy is an exteneive property and hence quantitative comparison of, free energies of formation of oxides csn not be mode in two different reactions involving different massea. Eroneous eonclusions may come out if care ie not tsken in standsrdising the two reactigns for the eake of eompanison. Free eneqgies sgn be compared ba.sed on one g mole of the reaetant metsl or product oxide or o)rygen gas. There is no specific bar 'on sny of these bases or nny specific preferance on scientific prineiples. The eonmon thing in all these reactions is orygen gas. This diagram is widely used to asseas the relative possitrilities of varions oxidation reactions with respect to one-anothen whether one particular element would be in a position to reduce the oxide of a different metal under certain

at

eonditioneennbedecidedbywritingthetwooxidetionregctionsand subtrgctingonefromtheothertoobtainthenetfreeenergychangefrom thie diagrnrn. In the process of subtraction the oxygen part shall get

eliminated, if the base is oneg mole of o:rygen' etraightaway.If this is not the base the two equations urill heve to be balaneed to get the same result. It is therefore easier to have the free energy of reactions plotted per g mole of oxygen. The resctiona on the diagram are written such thst the reactant is one g mole of oxygen snd the equivalent metal and oxide are a{iusted aecordinglY' 2Mn + $2 = 2MnO aa

11. on the whole a huge smount of informstion is stored in this eompact

diagrem.
way this intormation has been exploited or is available for such use shall be deah with in the sections to {ollcnrv. nominalExample 14.2 : Steel is made by preferential oxidation of impurities in iron of the
The is supplied composition C-4yo, Si-1.5%, Mn-0.7/o,P-0.35% and balance iron' lf pure oxygen impurities. of these elimination of sequence to oxidise these find out the theoretical

si+ 02=siQ 4/gAt + 02 = 2/3 Alz Oa

Giren :

'

(1) 2<C> + {Oz} =

2{CO}

AGo =
170

-58800

31.97

(2)

[Stl

{Oz} = <SiOz>
AGo = - 217N0 {Oz} = <MnO>

+ 48.87

(3) 2[Mn] +

AGo=-190800+ 39.257
64.57 Solution : The {ree energy changes at 16000 C, the usual steelmaking tenrperature, are found to be AG8 = -118500 caUg.mole

(4) vs[P] + {Q} = 26 < Pz Os> AGo=-93100+

AG$ =-125600 -doAGR/n

= -117300 -do-

AGF= +277A0 -doAssuming the product oxide activities to be unity in all the cases and that the oxygen activity shall be the sanp in allthe cases that element shall oxidise first whose equilibrium partial pressure shall be the minimum" lt also means that the sequence of oxidation shall be in the order first that element whose free energy change on oxidation is the minimum. Therefore the strict sequence shallbe first silicon, then carbon, then manganese and lastly phospho-

rus. ln fact the first three are so close that they may oxidise simuftaneously and for phsphorus oxidation to be possible the activity of the oxide will har,e to be made rnore negative to make it possible.

t4.s"i

*i'}.l=RMAL

DOSSOCIATION OF OXIDES

!i has already been noted that in a standard Ellingham diagram the oxide lines slopes upwards from their plvots at AGo = AHo at zero degrees absolute. lt means that as temperature rises the AG vaiues becorne less and less negative. A situation can arise when the line intersectthe horizontal line at AGo = 0 t.e. Poz = 1 atrnos at sorne tenrperature. When it does so it means that the metal and metal oxide are in equilibrium at one atmcspheric pressureof oxygenandtheAGo = 0.ln reality in asystemopentoatmosphericairwherein poz = 0.21 the non- standard AG = 0 position rnay be reached much earlier. Any further rise in temperature would make the AGo now + ve, reaning thereby that oxidation ol metal
is no longer feasible. On the contrary oxide shatl dissociate into metal and axygen. ln fact this is the ideal process of extraction of metal from its oxide merely by heating, provided it is

possible to separately collect the metal so reduced. The process can be typically illustrated by the exarnple of silver oxide. (14.25) 4 <Ag> + {O2} = 2<AgzO> For

*730CI + 15'76 T o' aGo = = Hence above 4620 K silr,er oxide shall dissociate into silver and oxygen. This process can be used for extraction of siiver from its oxlde merely by thernal dissociation. Unfortunately silver is not available as oxide, at least not in naturai forrn, to make it a commercial

and

at

-f.?*:

possibility.

17',|

Theoretically allthese lines which originate from belor point O in the oxide Ellingham diagram shall intersect the AGo = O line at some temperature thus thermally dissociate at above that temperature where it intersects the p9, = 1 line. ln normal atmospheric air the

situation shall change accordingly. Normally these temperatures are fairly large and ewn if the oxide dissociates at such high temperatures it will not be possible to collect it in pure metallic form because of its highly reactive nature at that high temperature. The end result may therefore be that the oxide does dissociate into metal and olygen at one moment and immediately there after, while trying to separate the metal, it gets oxidised and producas
oxide again.

Similar considerations are possible for other diagrams as well. Mercury occurs in nature as Hgz S (mineral cinnabar) and has only small -r,e value of AGo of formation. lf this is heated around 5000 C it does dissociate into Hg and S, both gaseous forrns, and can be condensed to recover Hg. This is used in commercial practice to win mercury from its sulphide ores.

14.5.2

INTERSECTING LINES ON ELLINGHAM DIAGRAM.

Although by and large the lines on the oxide diagram belcnar the melting point of both the metal or its oxide are parallelto each other, their slope undergoes changes at the.melting or the boiling points of the metal or its oxide. Since the melting and the boiling points for dlfferent metals are quite difierent, the change in slope in these lines takes place at different temperatures. The slopes also change when phase transformations in solid state occur. The net result can be that some lines may intersect eaih other at sorne temperatures. The intersection changes the relative positioning of these lines and thereby its relative stability. lt means that AGo values relatively change their order on changes in the phases of the reactants and the products. The situation is described 6 qualitatively in Fi9.14.10. Let us asc sume that the two lines of oxidation of ld 2 metalA and B intersect at temperald ture f K as shown. Therefore belorrrr !J ld the temperature 'T A-oxide is more G Ir stable, being lower, than B-oxide. But after the intersection i,e. above I I temperature'T the situation is justthe reverse. Hence belour 'T reaction of

TEMPERATURE O11+
Fig. 14.10 - Intersecting lines on the Ellingham

'

dingram indicating the reversal of relative stabilitics after the temperaturc of intersectbn.
172

reduction of A-oxide by B is not possible whereas above temperature'T it is readily feasible. Such situations can be gainfully exploited to carry out certain reactions which otherwise

ar not possible below a certain temperature.

This is possible because, free energy consists of two parts, one enthalpy and thn other entropy; enthalpy being substantially constant with temperature but entropy changintn with temperature. The situation beconres so favourable after a certain temperature that thrlr net resutt in these two different cases is rer,erse. This will be disussed further again later.

14.5.3 Carbothermic Reduction of Oxides The efiect of intersection of lines on the oxide Ellingham diagram has just beeur discussed. The C-CO line is such that it cuts across lines of many oxides of interest. Th+r
slope of C-CO line is reverse to those of other oxides and therefore it should be possible tn reduce many oxides by carbon above the temperature at which the C-GO line intersectui their oxide lines. lt is thus possible to reduce the oxides of copper, lead, iron, nickle, coball,, molybdenum, tin, phosphorous, zinc, chromium, manganese; vanadium, tungsten, silicon,, magnesium, aluminium, calcium and so on at increasing temperatures in that order usinl;; carbon as a reducing igent. Carbon being rery cheap, in the form of either charcoal or cokrilr is used in fully exploiting this technique for commercial production of these metals from theil' oxides. Metals like aluminium or titanium can not be extracted by carbon reduction becausrrr these metals react with carbon and the product obtained is in their carbide rather than thrr metal form. ln some cases the temperature required for reduction is so high that it is not irr cornmercial proposition against other cheaper alternatives.

These reduction processes have to be carried out at high temperatures and hencril

gffi '"",T:-1tr""::'.i:ff ffi:J,"fl1"J[;i..:rnwhichsoridsiricawourduereouJerr

by carbon to produce liquid silicon. Given

2<C>+{Oz}=2{CO}
AGo = -53400
<

41.9 T cafg.mole

Si> =

(Si)

AGo

10050 +
43.3

--do-

<Si>

+ {Oz} = <SiOz>
AGo = -208000

..do..

Solution

From Hess's law for the reaction

<

SiO>

2<C>

(Si)

2{CO}

AG = + 208000

+ 162600 = -

43.3

T+

10050

53400

41.9 T

85.2 T
l:

T=

This reaction shall be in equilibrium when AGo = 0 and therefore this will happen a 16350 Cwhich is the minimumtemperature atwhich carbonwill be ableto reduce solirll

silica.

173

14.5.4 Metallothermic Reduetion of Oxldes

The fact that oxide whose line is belour is more stabler than that whose line is relatively abo\E can be utilised in devising processes to reduce ofdes that are above by

the metalwhose oxide is belcnltr. Example14.4: Thusif 2<Mn> + 02 = 2<MnO> lGfts.zol = -184000 + 34'63 T <Si> + Q and = <SiOz>
aG?r+.zzl Hence the free energy for reac{ion

(14.261

(4.2n

208000

43"3 T

u
(14.28\

2<MnO>

<SiU>

<2Mn> +1$ioz>
8.67 T

is obtained by subtracting one from the other as

AGtre.zel

= -24o00 +

or
Since this is negative
silicon.

AG?eoo"t<

= -10128 caUrnole this reaction is {easible or manganese

oxide shall be reduced by

Similarly commercially uranium oxide is reduced by calcium to produce uranium. There are many such commercial processqs. The thermit process, wherein iron oxide is reduced by aluminium to produce molten iron, which is used as a filler metalfor welding large objects. Ferro-alloys which are nothing but iron and some other metal combination like, feno- manganese, ferro-chrorne, ferro-silicon, ferro-aluminium, ferro-titanium, leno-tungsten' feno-rnolybdenum, ferro- nickle and host of such alloys which are produced by using reducers like Si, Al, Ca, etc., individually or in combination, to reduce their oxides. The reducers so used have fairly negative AGo values of oxide formation as compared with the values of the oxides to be reduced. ln other words elements at the lcnrer side of the diagram are used as + reducers to reduce the oxides which are relatively above.
Example 14.5 : Example given in Section 2.10.2 may be recalled here. lt was for calculation of enthalpy. ln place of AH if AG values are inserted it could show the method of calculation of metallothermic reduction of oxides.

The pattern of lines on the standard Ellingham diagram is well established since the reactants and the products are assumed to be in their standard states i.e. al unit activities' What will happen if the activitiqs are less than one r.e. the reactants and the products, individually or both are under non-standard conditions? The fiee energy change for the reaction in Fq.

'4.6

ELLINGHAM DIAGRAMS FOR NON.STANDARD CONDITIONS

(1a'1{

is given as

AG
zero and

AGo

RT ln

aM

-,1?x pO,

lf all the reactants and the products aFe in their standard states then the RTln term becornes

AG =
But if M is not in standard state then

AGo

174

AG

l= ld + RT ]n aM x
*+*

pOz

The values of the product

depends only on temperature'because it irrii

orcE'e'n nothing but equilibrium constant. and whose value is fixed for a fixed temperature' ln decreasesli' M of activity if even quotient sanp the to maintain the value of K i.e. the above then tlit'llr the po, will harre to increase. ln other words if the activity of reac'tant decreases i1 equlibrium partial pressure of oxygen shall proportionately increase. By the sane logir:r po, woutl|il value the reactant ac{ivity is unity but that of product oxide decreases then the

decrease to maintain

words the
decreases.

quotient the same for a fixed temperature. ln othe'r equilibrium partial pressure of ox.ygen shall decrease if the prgduct actirrity

the value of the

r: The situation is shown in Fig.14.11 by plotting the standard AGo vs'T line ior "'Arl" point by line on this generalised reaction as in Eq.(14.14). The tenperature T is marked This point is connected to point O, which when extended upto the p6, axis shows lllht: activity cr'l' corresponding Poz value as depicled by point'A. Because of decrease in the reactant (metaq the equilibrium pe. increases to say 'B'value. The'straight line ioining T. lf lhisr with o has a free energy value equivalent to .point B at the same temperature exercise is repeated for several temperatures the AG lor this non-Sandard oxidatiicrnt change even irl reaction as it varies with temperature shall be available. The enthalpy
1[l

!o :

d-l
d (,
o.'

PRODUCT

,tr",ys

I-

t*".iXotrRE
Fig.14.tI

oK

The rotation

of lines on Ellingftam
175

diagram

when the activities of prod'ucts andlor the reactants change'

non-standard conditions rernains the same since it is independant of activities. The nonstandard line is thus shownoriginatingatthesarnepoint i.e. atAGo = AHo and is shourn ts one passing through the point B. By the same logic when the activity of product oxide decreases keeping the nretal activity at unity the line originating at AGo = Al-.fo and passing

through point C shall be obtained.

ln fact these findings can be qualitatively stated as : 'lf the activity of the reactant decreases the standard free-energy-temperatureplotshallrotate anti-clockwise and if the product activity decreases it shall rotate ln clockwise direction lrom the plvot, AGo = AHo on the free energy axis.' lf both,theactivitiesoftheproductas well as thereactantdecreasethentheresultant

be the final state of affairs. Coincidentally it may so happen that their variation cancel each other and the standard line may rernain the same even in the
of their effect shall
non-standard conditions.

14.6.1 Specific Non-Standard Reactions

The rotation of the standard line on the Ellingham diagram because ol non-standof the reactant and the product may lead to drastic changes in the positioning relative of the various lines. lf the relative positions of the lines undergo reversals, the processes otherwise not possible, may becorne possible as was shown in Sec 14.3.21or intersecting lines. Severalsuch processes have been developed and carried out in practice in non-s{andard conditions, which otherwise are not possible under the standard conditions. Some such specific cases are dealt with belovv.

ard conditions

isafactthatsolid MgO isfarmorestablethanSiOz and hence solid MgO cannot be reduced by silicon at any temperature. But if the activity of SiOz is decreased by combining it with CaO the standard line of Si-SiOz rotates downwards considerably. At thesametimeifthe activity of magnesium isdecreasedbyusingvaccumthentheMg-MgO line rotates upwards. The net result is that the two lines intersect each other at a much
It
lcruver

temperature and the process:

_FeO + Mg (vacuum) Vapour Dolomite Feno Silicon Slag Silicab s readily possible and is carried out under vaccum at around 12000 C commercially to produce magnesium. This is known as Pidgeon's Process. The relavent thermodynamic
CaO. MgO

+ Fe.Si =

Ca0-SiOz

data are

2{Mg} + {Oz} = 2(MgO) AGo = - 358700 + 102.67 cailg mole < Si> + {Oz} = SiOz
AGo

(14.2e1

(1e.30)

= -208300

43"3

cal/gmole

Therefore the reaction (14.31) 2< MgO> + < Si> = < SiOe> + 2{Mg} (1 arnos) is obtained from combination of ( a.291 and (1 4.30) . lf the reaction is to be carried out under vaccum of 10 atmosphericpressure then (14.31) will reduce to ' (14.32l. 2<MgO> + <Si> = <SiOz> + 2{Mg}ro-3atmos
176

The
and lqr+.sA

aG?r+.ga

= lG?t+.so) -

aGfra.eg (14'33)

Gfr+.sg

Gfrq.ag

+ RT ln pMs

putting the actual vralues it becomes

=+ =+ =+

130400

2<MgO> + 2<CaO> + <Si> = <2CaO.SiOz> + 2{Mghc'.tno" (14.34) (14.35) z<CaO> + <SiO2> = <2CaO.SiO2> and therefore lGfra.sq = -30200 - 1.27 and hence lGtra.s4) = AG(r+.sz) + AGlt+.ss1 = + 100200 - 71.82 T

lf CaO is added to the reactant the resultant reaction would be

130400 130400 -

59.3 T

RT ln 10 59.3 T + 4.575 x T x 59.3 T - 13.72 T

(-3)

Atequlibrium or

0 AGlr+.3+; therefore the temperature at which equilibrium holds true is

+1100200-171.82T=0 T=13950K=11220C

No wonder in commercial praaice the extraction of Mg is carried out around 12000 C under a vaccum of 10 atmos. This is shown in Fig 14-1.2

The other typical example is reduction of silica by high manganese feno-managanese. The silicon line is well belorr managanese line in a standhrd Ellingham diagram - !50

i:...--/-"
-2o0

to
d
d lJ

e{F?}.

filfi"Jil?l-l# {ott*<?
o,

!-o

o,g

k-3 *.ti \T{l ,6$ ',;{J;' ,/+S 9-

;e.t

{Pl

-3oo
500

1000 ,5o0 TEMFSRATU;,g c11 ---.e

209.0

Fig. 14.12 - Free etergl consi.derations in the Pi.dgeon process for the extruction of magnesium by reduction of magnesia by silicon.
177

and therefore reduction of solid silica by manganese under standard conditions does not arise. However if silicon is dissolved in iron the activity of silicon is reduced drastically and hence the silicon-silica line shall rotate upwards. Concurrently as the MnO activity is reduced because of its conbination with silica as manganese silicate the Mn-MnO line shall
rotate downwards" The net result is that the two intersect at resonably 1000o K and hence it is possible for the reaction

lol

temperature like

[Mn]re-un

[SiOz]sand mould

= [Si]re-un +

(Mn0-Si0a)sus (14.36)

to occur in real practice. For the reaction

2[Mn]+{Oz}=(MnO) AGlr+.sd) = -162200

25'25 T (14.34

and
hence for

[Si] + {Oz} = lSiOz) lG?t+.sa = -215400

47.73 T
(14.38) AGo 6a.sz;

!{Mnl

(Sioz) = [Si] +Z(MnO)

AGo 1u.ae;

The equlibrium constant of reaction (1a.38) is

= AGo (14.36) = + 53200 - 22.8 T

(r+'ss;

3si)x a(Mnoi = a(MnCl x a(Sioz)

(i)

[%Sil

[%Mn]:fufr

:fsifxNrr,tnoz' yr,,rr6, 'fsioz

Nsioe

Assuming approximate values as

%Si = 2%, fs = 0'005 (ii) oh Mn = 75"/o fun = 0.01 (iii) Nuno = 0'1 Y Mno = 0.5 (iv) Ns1s, = 0.9 YSio2 = Q.g
K1ra.sel

Putting these values in equation (14.38) gives

approximatelY 10-s

= AGftc.sol + RT ln K AG(r+.ss) (16000r; = 16800 + 4'575 x 1600 x log 10-s approximately = - 20OO02al Slnce free energy change is fairly - vetne reaction of reduction of silica by Mn is possible
AG6e.se1
and which is shown in Fig 14.13.

14.6.2 Reactlons Under Vacuum

This belongs to the category of reactions under non- standard conditions but being of its own type has been described separately. Pressure is also one of the standard state and 1 atmos. is taken as the standard state for plotting the Ellingham diagram. lf the reactions are carried out at less than 1 atmos l.e. under vaccum or at higher than 1 atrnos pressure the standard [ines, since all of these reactions involve a gaseous component i.e' at least 178

f g

x og-

.9

Fig. 14.13 - The free energl-temperature relationships ind.icating

the possibility of reduction of silica by manganse.

oxygen, undergochangeswith pressure. Forageneralreaction as shown in Eq. (14.14), if pressure is reduced, the oxide would tend to get reduced and produce metal and vice versa. But when the metal and its oxide are not at unit activities and in that case if the orygen partial pressure is decreased then the equilibrium shall move in such a way as to maintain the equilibrium constant the sarne and vice versa. Pressure is important when gaseous product is formed in these reactions and which possible only when carbon-monoxide or carbon-dioxide are fornred. Carbon dioxide is is not a high temperature stable phase and hence only monoxide is considered here. The decrease in the partial pressure means decreased pco and hence for the same activity of carbon the equilibrium oxygen partial pressure has to decrease orthe C-GO line shall rotate

in clock-wise direction. lt means that this line shall cut the oxide lines at still lorer ternperatures and thereby make the carbothermic reduction possible at lorrrer temperatures. lf the prssure is increased aborre one atmasphere then just the reterse shall happen. It also means that at lower pressures r.e. under vacuum carbon will be readily oxidised by oxygen and that the product of activities of oxygen andTarbon shall be decreased. This isfullyexploitedincarryingouteitherdecarburisation ofsteelmeltundervacuumby supplying oxygen or deoxidation of steel batrr by supplying carbon readily. This is what is known .as vacuum treatrnent of rnohen steel. This pressure dependency of carbon oxidation reaction can pose serious threat because of the possibility of disintegration of refiactories (oxides)
by carbothermic reduction under vacuum.

179

Example 14.5 : Find out the levels of carbon that can be achiewd when molten steel is decarburised by supply of oxygen at 1 atmosphere pressure and under vacuum of 10 atnnsphere. Girrcn : The oxidation of carbon in steel rnelt takes place as

and

tcl +[ol ={co} logK= #2'69 or

2.191

Solution: Thevalueolequilibrium constant at the steelmaking temperatureof 16000C

or 1g73o K is given as log Ktezsox =
KtezsoK

= 2.02 x 10 atrnos.

K can also be expressed for the above reaction as

Pco '. = atclr ..(o)

The level of oxygen in both the cases shall be proportionalto the oxygen pressure supplied and it is the same in either case and therefore the carbon level achievable shall be proportionalto the pressure of carbon monoxide in the surrounding atmasphere. Therefore assuming that Henry's law is obeyed then

K(rarnos)

=*gt'7q

=2.o2x110

therefore %C in steel melt at under one atmos will be about 0.3-0.4% and %C in steelmelt at 103 atmos will be about 0.1 This shows why vacuum treatrnent is given to steelto reduce carbon to a very otherwise is not achievable in open atnnsphere.

lcnru

level, which

14.7

CONCLUDINGREMARKS

The free energy temperature relationships in the form of Ellingham diagrans is a fundamental knowledge in the understanding of oxidation-reduction reactions for predicting the equilibria and which in turn is essentialto understand the smelting and refining processes.

I
I

180

CHAPTER

t5

KINETICS OF PROCESSES

rates of reactions
15.1
INTRODUCTION

So farthe reader is quite conversant with state and path properties. Therrnodynarn ias mainly deals with state properties and the conclusions therefrom are independent of path

Taking the example of overhead water tank, one can say that the,energy exchange associated with the transfer of water from tank to the ground level is fixed no matter whether water florls down, via 15 m,m dia pipe or 100 mm dia pipe or 'through a nanow capillary like tube (disregarding the frictional component in each). Whereas in each of these cass the tinre required forflorr of a certain annunt of water depenCs on the path r.e the dianreter of the tube carrying the water. The rate of flcnv shall further get complicated if the section of the tube was non-uniform and having various restrictions in the form of bends and the like. The rate of flow of water therefore is a path function. The study of rate of any such thermodynamic change constitutes the subject matter of the field of 'kinetics'.

of the process.

The study of rates of chemical or physicochemical processes ought to be very rigorous and in detail in order to appreciate the processes and evaluate the time taken for a certain change to occur. Conversely during a certain time interval it would be possible to evaluate the extent of change that might occur, from such kinetic studies. The industrial or commercial reactors wherein the processes are carried out ln actual practrce, are often fairly complicated and quite often these are studied in simplified models in labooratory and the findings are compared with the cornmercial results to assess the clqsseness of suclr
simulations. The possibilities of a process occuring tn practice is indicated by its - ve free energ,* change or decrease in the free energy. ln reglity a thermodynamically feasrble process may occur so slowly that apparently it might give lan rmpression of not occuring of all, The fact, in such cases, is that the processs is taking place at so lovv a rate that within the reasonable time no perceptible change is observed. This is best illustrated from the example of a mixture of Hz + Oz contained in a vessel. Factually Hz and Oz are reacting but the rate of such reaction is egligibly small.

Kinetic, studies

may be performed under 'steady' or lunsteady' status oi

the

system. At this stage the discussion is confined to steady state condition only. Processe*; if occur within a single homogeneous phase, the study rs referred to as study of kinetics ol

homogeneous reactions but if it is between two or more phases then it is a case of ktnefics of hetrogeneous reactlon"
The honngeneous kinetics is quite uncommon whereas heterogeneous kinetics is normally possible. The examples of systens like solid-solid, solid-gas, liquid-liquid, etc. are all examples of heterogeneous systems. Sonretimes a new phase is forned during the process and hence the role of nucleation and growth may dominate the kinetic studies in such cases. The formation of CO bubbles in steelmaking, precipatation reactions, etc. are typically the best illustrations of this category. Since kinetics is path dependant, the process may be sub-divided into various sub-steps to make up the oterall process. These are called elementary or kinetic steps. This is referred to as study of mechanisin of reaction and rate of the change in each of these sub-step may not be the sarne depending upon the nature of these sub-steps.
ln such a case the overall rate of the process will be dictated by the rate of the

slorest

rate of the rate-controlling step is virtually the maximum rate the process shall exibit approximately. The aim of the kinetic studies ls therefore to know the overall rate of the process under a given set of conditions (i.e path), to evaluate its mechanism and therefrom the rate controlling step and, to predict the condition under which the rate controlling step would be enhanced to achive hlgher overall rate of the process. The rate or velocity of a reaction is defined as the rate of change of concentration
(decrease generally).of reactants and (generally increase) of products of the reaction. lf 'C' is the concentretion of the reactants then the rate is given by -dC/dt. The reaction rates of some reactions like the thermit reaction may be extremely fast or for others may be quite slol. lt is a common observation that the rate is a function of concentration and temprature.

kinetic step in the overall path. This is known as the rate controlling step and which is revealed through the study of rnechanism of the process. ln a given overall mechanism the

15.2

KINETICS OF HOMOGENEOUS REACTIONS

The reactions which take place within a single phase are known as honrogeneous reactions. Solid state honngeneous reactions are just not possible. Liquid-state homogeneous reactions may occur but rather uncommon. However gaseous homogeneotrs reactions are not only possible but numerous. e.g 2Hz+02=ZHzO at sorne temperature abore 1000 C or Hz + Cl2 = zHC/. and so on. These are often catalytic reactions meaning thereby that catalyst help the reactions to occur readily i.e accelerate them immensely.

15.2.1 Order of Reaction

The sum of the powers to which the concentration of the reacting atoms or molecules

that have to be raised to determine, the rate of'the reaction is known as the 'order of reaction'. The order of a reaction is quite independent from molecularity of the reaction. lf the process is expressed as

aA+ bB+

product.

(15.1)

then the rate of the reaction is expressed as

182

dc
dt

kx

Cl,

CB.....

(1s.2)

where k is the 'velocity constant or specific reactlon rate',

or 'rate constant'and Cl

areconcentrationsattimet. The valueof(a the reaction.

For a first order reaction

C8,...,

+ b +....)lsthentheorderof

- *

= *'

Ce

x ce ......

(15.3)

and since the concentrations of A or B or .... are going

to vary in proportion to one another

(1s.4)

-#
-,f
r,

= k x cn

= kJidt OnintegrationwithinlimitsC=Cottt=to and

{15.s)

Q=Q at t=t
if

= 4Q t

rog;L ( -Uot. Similarly lor a reaction

the higher

(15.6)

where r is that amount of C reacted in tinre

-ft=kxcsxpe -9= dt dt

(15.7)

shall be a second order reaction. ln this way

order reaction can be evaluated.

The order can be zero also if the rate does not depend on concentration of the reactants. Also it can be a fraction depending upon the reaction'

Far a
exists betweep

zero

121 - r)121 and hence t vs. [CY'? - Co -4 should be a straight line Likewise for first order reaction drldt = k(Co-$ or R = 1ltflog (ColOo-r)] and t vs. ilog (Co /Co - r)] should be a straight line relationship. For ond order reaction drldt = k (Co-r) 2 or ft = 1A [r/Co (Co-r)] and tvs.[r/Co (Co-r)]

k = Zlt pf -

order therefore dr/dt = k or k = rlt and a straight line relationship and t. For a half order reaction drldt = k (Co - r)V2 and
(Co

has to be a straightline relationship. The order can thus be verified from experimental data by plotting the respective variations as a function of time. For example if log flog (Co /Co - 0l vs. time is a straightline it is first order process and so on. n Example15.1 : Therate constants for the lea'ching of alumina inaqueotrsNaOHsolution at different temperatures are :

logk

where k is the rate constant and T is in 0o K. Calculate the activation energy of the process, Solution : According to Arrhenius equation on log scale

1/T x 103

-12.9 -13.1 \13'3 -13'5 -13'7 2.40 2.45 2.25 2.30 '2.35

-13.9
2'50

logk=losA-q'?'+
where the factor 0.4342 converts the natural log

to log to the base ten.

103

The slope is thereforer

equalto -13.1 + 12.9

2.fi

2.25

x103=-4 x
183

This is atso

equatto

g*,? x e from the equarion and

e = -4 x 103 or e =
-1go0ca/gnnle.

hence
The

Time %wt

solution : The data are anarysed further by evaruating the foilowing varues

certain temperature. Time min. %wt lms (cumulative) (the %wt loss shown above is of reactant). Find out the order of this reaction and ado find out the time required to achiere 50% of the reaction.

- \ nature of the slope in this exercise. The data are such that the same value is true even if other pairs are taken into account because the relationahip is exact straight line. Example 15'2 : For kinetic studies of a certain process follorruifig data were obtained at
ve sign indicates only the

248121s202s35 1527385263779299,

min. loss

2 15

(unreacted)

{reroo-r) Bs zs 62
(Co

(cunu.rlative)

4 27

B g8

12 52

15 63

20 TZ

25 gZ

3s
99
1

4s

sz

zs

log Co/

pY - (co-+)ral

- r)

7.36 1.e8 i wr - (co - r11t21 ols o.ss o.ss 0.51 o.ss 0.4s 0.s7 0.51
F,

fr tc.-rt

o.7s 1.6 2.1s 3.08 3.s2 4.81 7.18 e 0.070 ,0.136 O.2OT 0.gl8 0.2131 0.638 LDzg 2
12'75 ts.71 23.56 24.s6 23.31 17.71

rr'P! = 0.562 Thesedataaredeveropedtoprotgraphs oftimetvs'eachone ofthevaluesgibeninhorizontat columnsasshown inFig. 15.1.

theaveragevalueof

lo?-(co-

gives that since in the graph prf _(Co_r)1pl vs.timet s almqst a straight line relationship whereas the other relationships are far aruay from this nature therefore the process must be an 'half order'reaction. Since for ,""ltion in" l-"," constant "urh /

Refening back the conditions for straight line relationships for certain order of a reaction noir

k - |
The tinre required

rc'*

(cq *,r;121 and since these varues vary to sonre Lxent the

a\rage value can be taken as 0.562. for loc* of the reaction to occur can be calculated by putting the values in the above equation wherein altyalues except that of time 't' are known as k is 0.562 and 'r' is 50"6 and Co is 100% and hence time t for 50% reduction = 10.42 min"

15.3

THEORIES OF REACTION RATES The earlier collision theory of reaction rates

occurs because of collision

of

is based on the assumption that reaction a reactant atoms or molecules with a certain minimum
184

4^

T
t g
AI

cl"

Fl1.-

of order of a reaction' 15.b Auantitative method for evaluatinn

intensityofimpact,Theminimumimpactenergyisnothingbutactivationenergyofthe it depends on the concentration (mass) and temperareacting atoms or molecules and place the successful in making the reaction take ture of the reactants. For collision to be Hence the rate atoms or molecules should be appropriate' orientation of the colliding -"-onr (15'8) atoms/moles/cc/sec Rate = Or tN".
same orientationprobabilityor stericfactor'Thiseqlrationhasthe

WhereNcisthecollisionpersecandQistheactivationenergyandopisthe form as that of Anhenius

equationwhereQpxNcisconstant,indicatingtheprobabilityofareactingparticlebeing activation energy Q' correctly oriented and possesbing the reaction Rates or Transition further modified into theory of Absolute
This is based on Arrhenius state Theory or Activated complexTheory. For a reaction barrier and principles of quhntum mechanics' This has been
-

concept of energy

A+ 8..".-C+

D'"^'"

sinto

asperthetheory,firstthereactantsformaactivatedcomplexwhichthendisintegrate other chemical has a very short life but it exists as any the products. The activated complex of the disintegration of reactants' The specific rate species and is in equilibrium with the
185

acti\rated complex is a universal rate independant of the volume of reactants and the complex fornred therefrom. The reaction path is often shown as in Fig.l5.2.

at energy level P indicating that P energy will be liberated. But before this can happen the reactants must acquire additionalenergy Q as activation enerqy and attain the activated leveli.e. the
as reaction occurs

It shows the reactants at energy level R and products

-*

-- T-=-

"l
6

Fig.

15.2

- The schematic path

z ur
PROOUCT ENREY LEVEL

llt

of the reaction showing energl barcier

the

REACTION CO.ORDINATE

activated complex of

energy Q +

is formed and then the reaction occurs to produce

product at P in the form

reactants +

activated

complex +

product

The net energy release is stillthe sarne. The reactants acquire this additional energy by way of mutual collusion and interaction. The reactant at tines may acquire additional energy
more than even Q. But if such a particle is not correctly oriented meaning thereby that the path is not due for conect collision the reaction may not occur. Hence for the reaction to take place

the minimum additional energy equivatent to activation energy and correct orlentation must precede the actual collision. The net useful equation finally has the form

Rate = T tG

This equation differs from the Arrhenius equation by an additional linear temperature term. But over a nanow temperature range the term 'T x l(s' can be treated as another constant and has thus the sarne form as that of{he Anhenius equation - which is therefore considered adequate for mqst purposes. The activation energy is equalto AH the enthalpy change in the formation of the acitvated complex. A reaction having a large negative free energy change can still occur very slowly if the activation energy is too large. The. reaction is still strongly temperature dependent because of the temperature dependent exponential term.

"-aFl'fir

(15.e)

15.3.1 Effect of Concentration on Kinetics

For a reaction A + 8...... - C + D +.."". Froward rate is K. Cc. Co...... and backward rate Ku . Cc . Co. , . , " where Ku and Kl are respectively the specific reaction rate constants of backward and forard reactions.

is

186

At equilibrium by definition ilself these two rates are same and hence

Kr

. Cn . Ce....'.

dividing one by the other

Ku .

Cc'Co..'.'

(15.10)

K {equili. constant)

(15.11)

For irreversible reactions the bachrvard rate is negligibly small and hence Rate = Kr Cn Ce. . . ...

(15.12)

15.3.2 Effect of TemPerature

From his experimental data, Arrhenius empirically showed that the rate of reaction is (15'13) Rate = AexpQRr givenas where A & e are constants. Now the meaning of the terms have been understood as A being the frequency factor or the probability of a reactant being correctly oriented on the reaction path wiih energy Q. The constant Q is now \nown as activation energy, the minimum of which must be possassed by a particle before a reaction takes place. Taking logarithm

log Rate = log A-CyRT which showsthat log Ratevs. lnverseoftemperatureshall be a straight line relationshiP. Reaction rates are measured at various temperatures and plotted as rates vs. inverse of temperature. The -ve slope of this line is the activation energy of the process. the diffusing specie is proportional to the concentration gradient and area across which diffusion takes place. or

15.3.3 Diffusion Laws The Ficks First Law states that the flux of
flux
where
,J'

J=-D!q dx

(15.14)

is the amount of material that diffuses per unit time in a perpendicular direction with

reference plane having a unit cross sectional area, 'C' is the concentration "nF

x is the

coordinateinthedirectionofdiffusionandDisthecoefficientofdiffusion'
Ficks Second Law states that

ac_na2c
At

-"

(15.15)

a'x

wherein dO/dt means the rate of change of concentration"

to thermodynamically diffusion shall occur only from where the cheniical potential is high for force driving the strictly gradient is where this is lcnar. ln other words cherflical activity gradient is diffusion to occur. This is rather complicated and hence simple concentration considered sufiicient to work out diffusion for general purposes.

The diffusion does not occur just because of concentration gradient. ln fact

15.4

KINETICS OF HETEROGENEOUS,REACTION$

The reaction which occurs between two or rnore phases are like reduction of solid iron of solid oxide by a reducing gas, between two immiscible phases like slag and metal, leaching phases ore by a liquid acid, distillition, and so on. ln this either reactants are from different the consequence as a phases and or the reactants and products are frorn different phases alone' reaction takes place only upon their contact i.e. at the interface of the two the ln either case the reactants have to be transported to the interface and then intereact for
187

reaction

to occur and

the products to be transported away from the interface. The proces.s

is known as diff*aon which is a result of rnorrement gradient. ln a liquid phase the mass transfer can the concentration down of atoms/molecules take place by either diffusion as well as by fluid florrrr in either lamellar or terbulant form. ln lamellar way the fluid moves in the direction of flovv and in terbulant by forming localeddies resulting in flow at right angles to the direction of flory'

of transportation of these takes place in various ways depending upon the nature of the phase'

ln solid state

this nrass transfer

15.4.1 lntedace of Heterogenous Systems

the two solid phases in the contact region. The story however is quite different if a fluid
phase is
A solid-solid interface is merely a contact without in any way altering the structure of

involved.

The velocity of the fluid in contact with a solid is practically zero, although the Velocity in the bulk may be a finite value. This is because the layer in contact with the solid cannot slip over the solid surface. lf it is so the flow would be a frictionless flcrur which is not the case'

Therefore there exist a velocity gradient from zero at the interface to whatever apparent value is there in the bulk. The fluid flow near the solid interface is thus lamellar and in the bulk terbulant with a buffer zone in between. Any reaction between solid and fluid phase therefore has to take into account this rrelocity gradient layer while considering the mass transport.

in the region of velocity-boundary-

This relative stagnancy of a fluid layer at the interface, affecting mass transpott also results in concentration boundary-layer atthe interface on the fluid side. lf both phases are fluid then this layer exists on either side of the interface. ln case of two fluid phases in contact with each other,the interface is not a plane; it is rather waly. There is likely to be a emulsion of both the phases i.e. dispersed phase at theinterface.Althoughthetendency of the interface is to remain plane (as minimum energy is associated with plane surface)
the eddies do not allow it to remain so.

The idealised structure of the fluid interface is shown in Fi9.15.3. Although the concentration varies continuously from the interface to the bulk, the actual contour is not
readily available for mathematical treatment. Therqfore a tangent drawn at the point of interface conccentration in the form of Ct -N is assunre'd to be the concentration gradient and the

Ca

is supposed to be the stagnant boundary layer for the purpose oi concentration

The concentration gradient can now be mathematically expressed as

assegsment

t-l - \rB
The diffusion ian be exPressed as

existing at the interface.

nux

J=DF=a)
the intLrface foi a two immiscible liquid phases system

The idealised structure of

is shown same in the bulk is the in Fig.15.4. lt is pressumed that the bulk concentration anywhere because of inherent terbulance.

188

A.r INTERFACE

CONCENTRATION

I z o

ACTUAL CONCFNTFA'tloN FADIEN'T

k G F z ld
(,

Fig. 15.3 - Concentration gradbnt

ASSUMEO CONCENTRArION

z o (J

in a hetero- geneous sYstem. The assumed concentration gradient is also shown by the tengent.

lf a reaction is to occur between these two phases then the reaction shall take place
in the

1. 2. 3. 4. 5.

folloting stePs : Tbansport of reactants from the bulk scross

the boundary layer to the

interface. Adsorption of reactants into the interfacial layen Chemical resction amongst the adsorped species in the inter{ecial layer
(bond sxsftqngie) Desorption of products from the interfacial layen Tlanslnrt of products across theboundary layer into thebulk.
,1

whole intedace and once covered fully further adsorption occurs with difiiculty. The transporl of the interface of reactants or products can be worked dut from Fick's lzurs. The fraction of the concentration in increase with covered by the chemisorbed reactants increases surface active reactants in the bulk phase' electric aK Example 15.2 : Find out the rate of desulphurisatisn of molten iron by slag in an fumace und the follorruing conditiohs

the Although physical aOso*ption ls possible, chemisorption is more dominant in the metallurgical world chemisorption is a irreversible process and it may tend to cover

[%S] = 0.067o lnterface %S = 0.01% Difiusioncoeff.of S = 3x10aqmz/sec Stagnant boundary layer thickness = 0'05 cm Average bath depth in the furnace = 20 cm dS n" x ACs/X g/cm2 /sec Solution : - "o dt, =
bulk metal
189

ca0I)

\
BULK PI.IASE

II
Fig. 15.4 - Idealised structure of an interface of contacting fluid phases I and II.

nrrnrace\!r{II)
ASSUMED STAANANT
oOUXDARY LAYER

ASSUMED EOUNDARY s?AqMNT LAyFR (E

(I'
Cgcl

SUt'(

FHASE

(I)

where Ds is the diffusion coefficient of sulphur in metal bath. x is the boundary layer thickness and ACs is the difference in concentrations of bulk and equilibrium or interfacial sulphur concentration. Conwrting this into more convenient form in %S

gives

-d%s/dt=DsxAcs/

r(#)

where p is the density of molten iron and can be taken as 7.5 glcc. Putting the other values in the above eluatiols";;;* = z x 1a4 o/orsec. or = 0.7 yorhr. Example 15.3 : ln the previous example find out the time required to attain 80% of the equilibrium.

Solution

!9
OT

= P.

ACs

/ x g/"-]/"""

converting it into more conwnient form using lo as

= Ds x

%s/x (o/1oo; glcnf lsec

Since change in 7oS in the bath changes the concentration gradient responsible for diffusion of sulphur into A%S, therefore

dt%sl

=9i#=-d[^%s] px d
d[A%sJ:1
100

or

ds = -

Px

putting this into the above gives

d,=lffiS'# or =#x drnt^%sl

gives

Therefore for a bath depth of 20 cm, boundary layer thickness of 0.05 cm and diffusion coefficient of sulphur of 3 x 104 and between the limits of [A %S] at t = 0 to be one to t = 158 mins. [A %S] at time t to be 0.20 (left orrer to attain equilibrium); it

190

15.5

in series for a process to occur the out of the above mentioned 5 consgcutive steps this or decided upon by the slc,vrrest step in overall rate o{ the process shall be controiled considered 4 are fast enough so that they are not series. ln general step No. 2 and step No. or transport mass are remaining' two

RATE CONTROLLING

STEP

-'

out of the as limiting tne overatirate of reaction. chemical reaction step' diffusion steps and the third one as activation energies and that step with These various sub-steps harrc their individual the the one limiting the orrcrall rate of the reaction' lf the highest activation energy shall be overall the fast enough slour, and the rest of the steps are chemical reaction the process is terrned and "u"n"i" "t of chemical reaction process rate will be controlled by the rate if chemically controlled process' on the contrary as under chemical control or it is
difusionormasstransportrateisslowandotherstepsarefastenoughthenthe mass transport or is said be a diffusion or process is controlled by diffusion or mass
transport controlled Process'

Thiscanbeexplainedintermsoftheflowofliquidinupsidedownpositionofa
bottlewhereintheflowrateiscontrolledbytheconstrictioninthebottleandthatconstriction thb flotrr'
of liquidfrom the bottle is controlling or the bottleneck in the overall flow

reaction' both are enhanced by increasing The rate of diffusion or rate of chemical stirring and it has nc rate of diffusion is alone enhanced by temperature or vice versa. But the
influence on the rate of chemical reaction' process anc slow step in the orerall kinetics of the It is very pertiment to indentify the removetl be bywhichthis bottle-neck step would therefromwork out the ways and means

bV under diffusion controll will be accelerated or diminished in its influence' A process I hastet only not diffusion' lncrease in temperature would adopting stirring which would hasten thtr control' the rate and if the process is under chemical diffusion but, if it is not controlling full/

These tricks have been rate as we, would;;;;;;;;"i"bta"temperaturerise. process techniques for improvin::t exploited in oewloping a variety of -.steelmaking kineticsofsteelmakingreactionsandtherebytheproduclivityofsteelmakingshops. as an indication of the type of contrtl Acwation energy values are often taken itis not possible tosimplil'r possibty existing in theprocess.lf theprocessiscomplexandif of activation energy values, the apparent rates vl' it for laboratory studies ior estimation

inverseoftempraturcarcplottedandfromthemon,theapparentactivationenergy|: in th ri indication of the possible control existing estimated. Even this gives approxmate controllt often taken as an indication of diffusion process. Low values of activation are proces-ses' The intermediate valutrri processs and high values for chemically controlled
be interpreted carefully' can however be misleading and should

tl:

15.5.1 Mechanism of.solid-Fluid Reactions

reaction is shown in Fig' 15'5' ln su';il The mecahnism of soild-fluid interfacial g",r assimirated in the burk fruid and :r reactions if the product of the r"".tion'i!'irriJi t: the reaction may be controlled by such transport transport through ut"g"nt fluid layer cQ as such' Gasification of-carbon by reactants or products or by chemicalreaction (15'1'il

'

as

-:c;

;'tCorl = 2{co}
191

reaction step. The other type is where product

is a typical example of this type and the reaction has peen found to be controlled by chemical

situation after

is a solid condensed phase and in that case the a certain amount of reaction has occured is shown in Fig. 15.6.

The reaction resufts in accumulation of product layer which separates the main interacting phases' Further reaction can occur only by diffusion of reactants across this product layer, in addition to the usual diffusion of reactants across the stagnant fluid layer. ln this case the accumulation may result in contraction of the area of original interface depending upon how the accumulation occurs. The shape of the interfacial area hower,er

lrl

3r
F

COI{C IN BUU

r
o.

ul ('l

I l> l{,

*\ l--t lc
trr

REQUI REI

DtFFust0r, -PAl.Hg

z
E

conc

INTERFACE

At ci
tt (,

o
Q

15

lr
Y
J

o.

IF l((.l t: lo lo cl al
l'lI FI
Jl

l-,

-.r
I

lo
I

BULK
FLUID

/ I

q
I

coNc. LJ

o
-.1

(,

d z c)

o o
I

AI

crl

'o 3i
Jl trl r+J

o-

o
(n

c,l

ltl

<l

ul
FI

tl
c6
I

(4

=l
Fig. 15.5 - The idealised corrcentration gradient in a soli"d-fluid system when the prdrct of the reacti.on does
nat accumulate at the interface.

3l EI f,l (, (,

FI zl <tr

I I

;tl

: 3 -,
It,

Fig. 15.6 - The idealised concentration

gradi.ent in a solid-fluid system when
the

product of the reaction does

accumulate at the interfaee.

same,as like the original. Such processes where the shape of the original reaction interface remains the same but actual areab altered are known as topochemical processes. The ray of such reaction will decrease continuously with the progress of the reaction because of increasing accumulation of the product at the interface. The reduction of Fez og/F3 o+ by H2 or Co gas is a typical case of this type. tt can be shown that if [1-(1-R1/31 vs' time is a straight line then it is a pro.""" .ontrolled by chemical reaction
ana if

remains the

tr{

-(1-R2/1 vs. time is a straight

line then it is under diffusion control; where F is

the fractional reaction occurred at time t. This is true when the reaction interface is well definsl

and rernains so during. the progress of the precess. Hower,er if the solid partigle is porous
192

then the kinetics will be afiected by the volume.

tortuoslty factor (interlinking of pores) and the pore

!

15.52 Nucleatton and Growth

lf reactions or processes resuh in the formation of a new phase then the nuleation and growth of that phase has to be taken into account while evaluating their kinetics' The nucleii are too small and reiuire volume free energy and interfacial free energies to be supplied from the pror,ss for its formation. lt is not easy to obtain so much energy and hence it is not easy to nucleate a new phase homogeneously. But if part of this energy requirememt The of nucleation is met by providing readymade interface the nucleation becornes easier. reaction prevent homogeneous can and necessity of hornogeneous nucleation is a barrier lf an from taking place at all. The typical case is ol carbon-oxygen reaction in steelmaking. to be interface is made available for this then the reaction rates hare been observed as reasonaly large. The rate of reaction of oxidation of carbon during steelmaking

slor when iron ore is added for its oxidation but when gaseous o{rgen is supplied gaseous for its oxidation it is much fasfier. This has been attributed to the fact that when but occur to reaction for the readily available oxygen is supplied the gas-metal interface is reaction ol this sluggishness this is not the case whLn iron oxide is added and hence the in the latter case.
is very

lQ+[o] ={co}

(15.16)

15.5.3 Reactlon Rates and Heat Supply

A process may be endothermic such that unless adequate heat supply is available the reaction may not take place for want ol heat. The case of carbon oxidation as in Eq, (15.16) in open hearth process of steelmaking where oxygen is made available from Fe2 Os , nnking the or,erall process occur as assured then only which is a net endotherrnic and hence simmultaneous heat supply has to be for the it may be under diffusin or chemical control. But if heat flow itsell is lacking be controlling willthen that rate heat the it is available diffusion rate or chemical reaction rate, ternperature difference the orcrall rate of this reaction. The rate of heat transfer depends on

geonretry and thermal between the source of heat and the reaction interface, physical of carbon can be eonstants of such a reaction. But the rate of such a reaction like oxidation reaction if exothermic a net into reaction enhanced by converting this net endothermic .13 that takes reaction the net when oxygen gas supplied in place of iron oxide for oxidation pucl is as giwn in Eq.(15.16) which is net exothermic in nature.

15.6

CONCLUDING REMARKS

The study of rates of procasses is a must for understanding the time required for the process carrying out such processesin actual practice. This has a direct bearing on actually<resuhed has econorny.The understanding of the rate controlling steps can and ir inproving the process economy by reducing the time required for carrying ot'tt these pr"*="* in practice. lt also indicates the practical limitations of improving the procss

ffiromy

by improving the productivi$.

193

Bibliography

Books recommended

for additional

readinE.

1. 2. 3 4 5 6 ? 8 9 Ls

ll

Physical Chemistry of Metals,

cG ran E

in

by L.s. Darken and R.w.curry,

1953 .

CfiemicalandMetallurgicalThermodynamics

and

II,

by u. L. Kapoor, VoI NaciandandBnos, Roorkee j,979.

ll ccril

lntoduction to Metallurgical rhermodynamics B ilf Tokyo, 1973.

by o. R. Garkerrr

ThermochemistryforSteelmaking

and. Ramkrishna Vol II,

by g. F. EIIiot, Irt. Gleiser, Addjrruweslr, London, 1963.

R. K. Dube, prgm@Or6d, 1977. OassicalThermodynamics by A. B. pippard - 1963. Physbal Chemistry of lron and SteelMaking by R. G. word, t&ronilAnoE, L962.
Upadhyaya and

c. S.

Problems in MetallurgicalThermodynarnics and Kinetics by,

LagEa'r

PlrysicalChemistryoflronandSteelManufacture, by G. Bodsworth, 1953.

ll{dlurgicalThermochemistry by

and C. B.

Alcock p(ges -

o. Kubaschewski, E. L.
19G9.

Evans

VoI I & fI Acadqbprres London,

Ptryshal Chemistry of Melts in Metallurgy by New

F. D. Richardson, york, 1974.

SYMBOLS

Activation energy Activity - Raoultian

Henrian

o
a
h
R

Activity coeffi cient

Chemical potential Concentration

aoultian

F{enrian

c
D

Diffusion coefficient Entropy Electrochemicai valency

Flectro- rnotivq-force

s
n

Equilibrium constant Entropy Excess proper$ Farraday's constant

.K
,

s
XS

r
A

Finite change in extensive property Fugacity Gas constant General extenslve property Gibb's free energy Gram l'{eat capacity Heat exchanged ${elinholtz {ree energy

t
R

z
G
g

c
q

A
U eii

lniernalenergy
I

nteraction pararneter

Meter
Mixing function

Partial property Specific heat constant volume

zM 2
Cv
Cp
o

cqlstant pressure Standard state with supe5;cript Specific rate constant Temperature degrees'absolute
degrees Celcius Volume

k oK
O6

Work done mechanical any other

w'

INDICATORS
Compositlon in.weight Gas

phase , Liquid oxide phase Molten metallic phase

Solid phase

percentages

wt%

{ ( t

}
)

ABBREVIATiONS

atrnm cal Kcal cc hr ln log min sec

atmospheric pressu.re calories kilo-calories cubic centimeters

time in hours naturallogarithm

logarithm to the base ten

time in minutes time in seconds

CONVERSION FACTORS
Farraday's constant, Gas constant

96,500 coulombs/g equiralent 23061 calories/volVg equivalent

R
pressure

l:3ii

":iT'tJ,,1li.es/more

82.07 cc atmos/de g/nnle 0.08207 litre atmos/deg/mol

ln
one atmosphere

2.303logro

'

;::[T
I

"n

,.,

,n,.,.,

1 torr]

1p33 g/cm2

ill

INDEX Enerry
Absolub

n"""tjorrni"
-

Theory-

185 185 186

altemate sources

Activated complex -

avail"bility
forrns

4
7

5,59
6
E

Activatbn enerry
Acti\dty -

coefficient determinatbn emf -

69,111,147 108,129 127,147

147 36 LL,24

prcpertbs sou:pes zero

bvel

7 70

Ebctochembalprccess

Adiabatic flame temperable -

t4S

Adiabatb Process Abha funcfron-

727,L}L
186

\t/

,,-dhenius
Boundary

equation -

hyerC

189

Cabric equatbn

18

Carbofirermic rcductbn -

L73
40 190 63

.,,4amotcycle

Chemicalconbol -

.nhembalpotentialof cell

L49

alapeyron equatbn -

ot
93

,_

Qldusius - Clapeyron equatbn Concenfuatbn cell -

LM
145
79

emfCriticaltemperature D Debye's temperahle -

28

DiffilsbnconbolDubng and Petitss law E

'27

190

Eirsbin'a theory of
specific heats 27

EbchbalworkLA.$ Ebchomotive force 145 coeffrcbnt- L49 -. 166 -?ningham diagem Electode pobntial L44 Enthalpy 5,20 g2 phase charge g6 reaction temperatue 29 g,48 Equation of State F4r'ilibrium L2,59 constant8g metastable ZB neukal7A pafial 1g stabb 7A thermodJrnarnb Lz unstable 76 Enthalpy 5,42 chembalchange 51naturalplocess 43 ' I phase hansformatbn I prlcess 51 randomness 45 temperature 48 zero level 7L '\ Excess,fi.ulctbn l4z
I

iv

Brbrrsive ppPedY F

9,59

Ivfiscibility gap Nfixing furctiorrs -

139

11ll
lii
'i3l

FandayFtcls law-

L48
187
15

lvlneupnic squaie Ivlobl quan&ies -

FtstbwFlee erergr -

Ivbbrquantities Mufti-compo
rre

63,102,12rEi

53 57
-

nt sohrtb n -

1ll

Gbbs -

N Nlafual process *.D6-ms't Ib at Theorem'

:litri

Ibbnhoh
ofnixing
F\rgacity -

56
LL7

6t I t:
1(,|i;t

66

Nucbation -

o
57

energr' - Duhemequatbn' -.e{* Gibbs ' Ilehnholtz equation'

Gibbs fiee

orrilerofreactbnOxygen potential P

1l:l;1

101, 125 66,87

1tl{ri

Partbl mohrProPertY'
19 108 26

63,101;ll
ll).1t.

lbat

caPacitst -

Ibruy's bwlbss's bw-

I
Heal sohrtion 104 9

Partblprcpe*Y' Path function' lPtrase mb stabrlitY -

rL

ril

i:ll:ll
'11,fi$

harsformatiors -

,lNlil

Inbnsive ProPerty' Inbrnal energr bobaric PrPcess' bochorb Pmcess bothermal Process -

Polbopb
Process

process -

11,:2iiri

5,L6,21
10

fureversible'
path -

,t,,$

LI,24'10,23

1{)

rcvesible'

1l:

K
I&netbs -

I(uchoffs hwI6PP rule -

151 33R 28
L

Quasi-chembalmodel-

l"Cl;

Ramsay-YoungRub -

(;#ii

:-

Iaws of &rermd5rmtttics -

Law' "fraouHs Rgubrsolutbn Richard's Rule -

:[ePl

liil0
(:}'ill

M
Maxwelfs rcbtiors -

'
!
:

lvletalb{rermb -

65s L74
V

Secondbw-

iiil[i;

i
I

Sieverf,s

hw-

113

Solil elecholte Solutbnmodeh Speeific heatCorstantvolune Corrsbntpressure Specific rcaetbn mte -

150 106 19 20 183 109

1"1

Stardad state Siate furctbn Sbady state Sublimation -

181

94
I

System

state T
Thermit process'Thermal dissocbtbn -

31

L7T
25 53 73 25

Thermochembky Tlremrodynamic pote ntial -

Third law -

Thrctling Tbpochemicalprocess Tlarrsport eonbnl Thoutan's Rub -

L92
191 96

-,rr{arft }bffequatbn'
Workfirrction-

vanderWaal's equatbn-.}

25

87,94

,w
57

Zeroth

bw-

76,77

vt

I I

Llt

ltl
It
Il
I

ilil
lirll It
lt LIL
I