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This book emerges from a long story of teaching. I taught chemical engineering
thermodynamics for about ten years at the University of Naples in the 1960s,
and I still remember the awkwardness that I felt about any textbook I chose to
consider-all of them seemed to be vague at best, and the standard of logical
rigor seemed immensely inferior to what I could find in books on such other
subjects as calculus and fluid mechanics. One of the students in my first class
(who is now Prof. F. Gioia of the University of Naples) once asked me a question
which I have used here as Example 4.2-more than 20 years have gone by, and
I am still waiting for a more intelligent question from one of my students. At the
time, that question compelled me to answer in a way I didn't like, namely "I'll
think about it, and I hope I'll have the answer by the next time we meet." I
didn't have it that soon, though I did manage to have it before the end of the
course. That episode convinced me that a discipline in which a sophomore, no
matter how clever, can ask a simple question which leaves the instructor struggling
for an answer is a discipline which needs serious rethinking.
In the early 1970s I had the great fortune of working with Prof. G. C. Sarti
at the University of Naples, and he and I (it was mostly his effort) succeeded in
making some sense, or at least so we thought, of thermodynamics. I was also
.busy writing a book on non-Newtonian fluid mechanics with my colleague
Prof. G. Marrucci, and I dared to volunteer to write a short section on the
thermodynamic aspects of the subject. It was not easy; one cannot deal with the
thermodynamics of non-Newtonian flow without understanding the basic con-
cepts of thermodynamics quite a bit more thoroughly than is required to simply v
vi solve elementary phase and chemical equilibria problems. The work done at that
time resulted in the publication of a short book (An Introduction to Nonlinear
Preface
Continuum Thermodynamics, SpA Editrice di Chimica, Milan, 1975), which deals
mainly with the thermodynamics of viscoelasticity. Chapter 5 in this book is a
spinoff from that book, but the material is presented here without the additional
complications of tensor analysis and differential geometry. Prof. Sarti took over
the teaching of undergraduate thermodynamics in Naples; he chose the approach
taken in this book, and was very successful in doing so. Unfortunately, he moved
to the University of Bologna shortly afterward, and his departure was a great
loss for the University of Naples.
In the late 1970s I taught for two consecutive years the graduate thermo-
dynamics course in the chemical engineering department of the University of
Delaware, at the suggestion of Prof. A. B. Metzner, who was chairman at the
time. I spent about half the time covering the thermodynamics of viscoelasticity,
and the other half on the more classical subjects of phase and chemical equilibria.
For that second part I prepared notes for the students; those notes constituted
the very first preliminary draft of this book. Little, if anything at all, has survived
from those notes to the present text, but the crucial ideas were developed at that
stage. For some time afterward I toyed with the idea of writing a book on
thermodynamics, only to find myself in a state of depression at the idea that
nobody would ever read it-there is no subject like thermodynamics to guarantee
that any two people interested in it will be at odds with each other concerning
how to teach it. But the small book published in 1975 got favorable reviews, I
got older and somewhat less touchy about what other people would think of
what I write, and in the early 1980s I started working in earnest on this project,
at the suggestion of Prof. M. E. Paulaitis of Delaware. Prof. Paulaitis has been
involved in this project for quite some time, has offered criticisms and comments,
and has taught with me a graduate course based on a later draft of the book.
Other people have been helpful in a variety of ways. Graduate students at
Delaware have offered comments on the draft distributed to them. Prof. C. A.
Truesdell read and criticized early drafts of the first chapters. Finally, Dr. R. E.
Rosensweig of Exxon Research and Engineering and Prof. Marrucci have
contributed the chapters on electromagnetic phenomena and on polymers.
Whenever I have taught a course on thermodynamics, I have begun by
presenting an overview of the discipline, and the Introduction is meant to provide
such an overview. I have also always asked the students to read a paper I published
in 1977 (Industrial and Engineering Chemistry, Fundamentals, 16, 138), which
deals with the historical and philosophical background of thermodynamics. A
grasp of the historical background of any discipline is, in my opinion, a useful
starting point.
... there ain't nothing more to write about, and
I am rotten glad of it, because if I'd'a' knowed what
trouble it WIU to make a book I wouldn 't 'a , tackled it,
and ain't a-going to no more.
Mark Twain
Gianni Astarita
Newark and Naples
CONTENTS
INTRODUCTION. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
Introduction
"Would you tell me please,
which way I ought to go from here?"
"That depends a good deal on where you want to go,"
said the cat.
Lewis Carroll
So far, we have discussed the architecture of this book; let us now tum our
attention to its scope. Writing a book implies that one has a certain type of reader
in mind. The reader is seen as a student of chemical engineering who has already
taken a beginner's course in classical chemical engineering thermodynamics,
where the skills of computing such things as simple phase and chemical equilibria
have been acquired. Those skills could be improved substantially with access to
modem computing facilities, and this would certainly be a fruitful area of writing,
but it has not been included in this book for two reasons. First, it is not the
author's area of expertise; second, the new edition of S. I. Sandler's book is a
masterpiece on the subject. This book is based on a different set of considerations.
Chemical engineering graduates will more and more apply their skills to nontradi-
tional problems: polymers, biological systems, and materials for the electronic
industry are just some of the most conspicuous examples. This being so has been
recognized in many chemical engineering departments, and special courses on
such subjects have been introduced covering these nontraditional areas. However,
we believe that also the core courses should reflect the new challenges facing the
profession; to quote from the dedication of the Lewis and Randall 1923 book
on thermodynamics, "the fascination of a growing science lies in the work of the
pioneers at the very borderland of the unknown, but to reach this frontier one
must pass over well traveled roads; of these one of the safest and surest is the
broad highway of thermodynamics." This means that the thermodynamics of
such nontraditional phenomena will need to be analyzed, and this poses a twofold
challenge. On the one hand, thermodynamic theory needs to be developed with
a methodology of broad enough generality in order to support its application to
nontraditional areas; on the other, some .elements of such applications need to
be discussed. As for the first challenge, it is hoped that the first part of this book
succeeds in presenting the appropriate methodology. As for the second challenge,
an attempt has been made at presenting some of the relevant material; we do
not claim to have exhausted the area (and probably it never will be), but we
hope to have achieved a first step in the right direction. One chapter is dedicated
to the thermodynamics of relaxation, which is crucial in the case of polymeric
materials, and one each to surface phenomena, dissipative processes, polymers,
and the thermodynamics of electromagnetic phenomena. In addition, some dis-
cussion is given of such matters as liquid crystals, biological systems, the con-
tinuous description of reacting mixtures, etc.
Consideration of biological systems brings into relief another important
point. Biological systems are never in equilibrium in a thermodynamic sense: the
equilibrium condition for a biological system is simply death. It follows that
either one abandons any hope of applying thermodynamic analysis to biological
systems, or one must regard thermodynamics as applying to nonequilibrium
conditions. The macroscopic theory of thermodynamics, which in large measure
is a theory of constitutive equations, imposes restrictions on the constitutive 5
equations describing irreversible processes just as it does for the eqUilibrium Introduction
constitutive equations. In both cases, it does not tell us what the constitutive
equations are, but only what they cannot possibly be. In this book, dissipative
processes are discussed in some detail, and attention is paid also to the question
of coupling between different dissipative processes, which is crucial in the case
of biological systems. The microscopic theory provides tools for predicting the
constitutive equations relative to dissipative processes, just as it does for the
classical equilibrium properties, and this is discussed at several points in the book.
Problems
MACROSCOPIC THEORY
Chapter One
NOTATION
Subscripts Superscripts
Thermodynamics, like any other science, makes use of a few primitive undefined
concepts, and both body and state are such concepts. A body B is endowed with
a fixed mass m" and occupies some finite region of space of volume V.. In
general, the volume V. will change in time, and so will the region of space
occupied by the body considered. [The subscript t (for "total") is used to indicate
that the whole body is being considered.] In thermodynamics, a body is often
referred to as a "closed system," i.e., .a system which does not exchange mass
with its surrounding, as contrasted to an "open system" which is some region of
space which may be occupied by different bodies at different instants in time.
We will use the symbol aD to indicate the instantaneous external surface of the
body.
Every branch of physical science is based on two sets of fundamental
equations. The first set is that of basic laws of physics, which are postulated to
hold valid for all bodies under all conceivable circumstances; the principles of
conservation of mass, of linear momentum, and of angular momentum are typical
examples. In thermodynamics, the basic laws are the first and seoond laws, which
are introduced in this chapter. The large majority of basic laws. of physics are
principles of conservation of some quantity (mass, linear momentum, etc.); the
first law of thermodynamics falls into this category, but the second law is an
exception, since it is not a principle of conservation.
The second set of fundamental equations are the constitutive equations:
these are relationships which are not supposed to hold for all bodies, but only
to describe the behavior of some restricted class of bodies, or possibly of a larger
class of bodies for a more restricted class of phenomena. A good example is that
of the mechanics of rigid bodies; it is of course obvious that there are many 13
14 bodies in nature which are not rigid (and perhaps one could argue that there are
in actual fact no bodies which are truly rigid); however, the theory of rigid bodies
Chapter One
is a useful abstraction which describes satisfactorily some phenomena as observed
in nature.
Constitutive equations are assumptions which may, or may not, adequately
describe the behavior of real bodies. In writing down constitutive equations, there
are several levels of assumptions which need to be made. The conceptually most
abstract level is the one for which it is postulated that some quantity is a physical
property of the body considered, and therefore its value depends only on the
physical condition of existence of the body' considered, i.e., on its state CT,. Such
quantities are called functions of state, or constitutive properties. If L is a
constitutive property, then the assumption that L is a function of state is equivalent
to the assumption that a mapping 1(·) exists which maps the state into the value
of L:
L = l(CT,) (1.1.1)
p = f(CT,) (1.1.2)
The next lower level is to assume that the state is uniquely determined by
the value of the total volume of the gas, V;, and the value of temperature. With
this assumption, the mapping f( . ) reduces to a function of two variables:
p = f(V;, T) (1.1.3)
The lowest level of abstraction is that where one assigns a specific mathemati-
cal form to the function f( .). For instance, one may restrict attention to ideal
gases; one can write
p = RTn,/V; (1.1.4)
where n, is the total number of moles of the mass of gas considered and R is 15
the gas constant. While it is generally recognized that there may well be gases
First and
for which equation (1.1.4) does not hold (i.e., it is clearly recognized as a Second Laws
constitutive assumption), it is less commonly appreciated that also equation
(1.1.3) is a constitutive assumption, i.e., that it may well be possible that a gas
exhibits a pressure which is not uniquely determined by its total volume and its
temperature. Incidentally, even saying 'that the body considered is a gas is a
constitutive assumption, since of course bodies which are not gases do exist in
nature.
In this chapter, attention is focused on those results of thermodynamic theory
which can be obtained by restricting oneself to only the highestlevel of abstraction,
i.e., by simply making assumptions about which quantities are functions of state.
These results are few: essentially, only the highest possible efficiencies of thermal
engines can be calculated. Few as such results may be, they are infinitely more
than in any other branch of science, where no results whatsoever can be obtained
without going down to at least the second level.
It is of course obvious that the state of a body may change in time, and that
therefore also the values of all functions of state will change in time. A process
is defined as the mapping IP'( • ) which maps time into the state:
O',=IP'(t) (1.1.5)
where t is time.
Now King David was old and stricken in years; and they
covered him with c/othes, but he could get no heat. Wherefore
his servants said unto him: "Let there be sought for my lord
the king a young virgin; and let her stand before the king, and
be a companion to him; and let her lie in thy bosom, that my
lord the king may get heat. .. So they sought for a fair damsel
throughout the borders of Israel, and found Abishag the
Shunnamite, and brought her to the king.
First Kings, 1.1-1.3
Since both q and Q are local quantities, it does not make much sense to ask
oneself whether they are or are not functions of the state of the whole body. As
will be seen later on, under some mild restrictive assumptions one can define a
local state u at any point of a body. When this is done, the heat flux q is taken
to be a function of the local state but the radiation density Q is not, as was
discussed in the preceding section. Equation (1.2.4) shows that therefore the
instantaneous rate of heating Qt is not a function of state.
P=Fov (1.3.1)
Forces acting on a body can be classified into contact forces, which act on
the external surface of the body, and body forces, which act directly on elementary
masses within the body (of course, there are also contact forces where one part
of the body does work on other parts, but these do not contribute to the influx
of energy into the body). The classical example of body force is, of course,
gravity. The total power Pt exerted on the body is the sum of the powers exerted
by all the forces cited above, and it can be regarded as the sum of the external
power PtE exerted by all contact forces acting on the surface of the body, and
the body power PtB exerted by all body forces. Ifb is the field acceleration (gravity
in the classical case), the body force acting on the elementary mass dm is b dm,
and therefore the body power is
(1.3.2)
where I{> represents the rate of change of I{> as observed by the elementary mass
0
dm. (A superscript· will always be used to indicate this type of rate of change,
called in general the substantial time derivative.) Thus one has
(1.3.4)
I{>t= L
I{>dm (1.3.5)
Kt=~ L
vovdm (1.3.6)
18 and thus its rate of change is
Chapter One
(1.3.7)
(1.3.8)
(1.3.9)
Appendix
It is important to realize that, in analogy with the total rate of heating Q"
the total net rate of work W. is not a function of state. The analogy is closer than
may appear at first sight. The reason why W. cannot be a function of state is that
body forces contribute to it, and body forces are active owing to the influence
of bodies other than the one considered (for instance, gravity is due to the pull
of the Earth). Contact forces are determined by the internal stresses in the body
considered (in particular, internal stresses on the surface of the body are the only 19
ones which contribute to W,), and internal stresses are functions of state, just as
First and
the heat flux by conduction; body forces are the analog of the radiant heat supply. Second Laws
Body forces do not perform any net work, but, by entering the momentum
balance, they contribute in determining the velocity field and hence the net work
done by contact forces.
In many textbooks on thermodynamics, the fact that the total rate of work
and the total rate of heating are not functions of state is expressed by the statement
that dW, and dQ, are not exact differentials. This statement deserves closer
inspection. Given a differential time increment dt, the corresponding differential
work done and heat supplied are, respectively,
and it is difficult to assign any mathematical meaning to the statement that these
differentials are inexact. In mathematics, the concept of an inexact differential
"form" is well defined. In its simplest form, given two quantities M and N which
are functions of two variables x and y, the differential form
is exact if a function F(x, y) exists such that its differential dF equals the
differential form (1.3.A.2). Since
We note that the question of exactness arises for the form (1.3.A.2), not for
dF itself; all differentials have full citizenship's rights, and therefore the statement
that dW, and dQ, are not exact differentials is, strictly speaking, meaningless.
Perhaps some meaning could be attached to it by somehow identifying the pair
x, y in the form (1.3.A.2) with the state, but this does not seem to be a fruitful
line of inquiry.
which is often more useful than equation (1.4.1). Also, for those cases where
b = -grad tP, with tP independent of time, substitution of equation (1.3.4) leads
to
which is very useful when integration over the residence time within an open
system is needed. Of course, equations (1.4.1)-(1.4.3) can be integrated over any
finite interval of time to obtain different macroscopic formulations of the first
law. Finally, equation (1.4.1), which applies to a body of finite size, can be
transformed to a field (oriocal) equation. Substitution of equations (1.2.1 )-( 1.2.4)
and (1.3.10) into equation (1.4.1) yields
r U' dm =
JII
JaR q' ds + r Q dm
JII
+ r w dm
JII
(1.4.4)
By making use of Gauss's theorem, the first integral on the right-hand side
is transformed to a volume integral:
which is the required local form of the first law. In equation (1.4.1), the internal
energy U, is regarded as a function of the state u, of the whole body. An additional
assumption is required in order to make the same statement about equation
(1.4.6), namely, that the internal energy density U at a point is a unique function
of the state in a neighborhood of that point, u. This assumption, which is generally
referred to as the principle of local action, is made in most formulations of
thermodynamic theory, but it is a restrictive assumption, since it excludes from
consideration long-range interactions within II: body.
For future reference, it is useful to define the local rate of heating per unit
mass, q, as
q = Q - divq/cI> (1.4.7)
whence the local form of the first law takes the simple form
U'=q+w (1.4.8)
S;~Jt (1.5.1)
The first and second laws are coupled if, as postulated below, the rate of
entropy supply Jt is related to the rate of heating Qt. In analogy with the conductive
heat flux q and the radiative heat density Q, an entropy flux J and a radiative
entropy density J are defined such that
(U.3)
j = q/T (1.5A)
J=Q/T (1.5.5)
S;~f
aB
(q/T)·ds+ r (Q/T)dm
JB
(1.5.6)
and two special forms can immediately be deduced. First, if the temperature of 23
all points of the body considered is the same (it may change in time, but is
First and
constant in space at all times), the "isothermal" form of the second law is Second Laws
Under the condition that q is zero throughout alB and Q is zero throughout
IB (note that Qt could be zero under far milder conditions), the "adiabatic" form
is obtained:
(1.5.8)
Occasionally, equation (1.5.8) is said to imply that the entropy of the entire
Universe never decreases-something that equation (1.5.8) does by no means
necessarily imply, and which anyhow is a claim of scarce pragmatic utility. More
concretely, equation (1.5.8) can be used as the starting point of a theory of
equilibrium, which will be called thermostatics. This theory is often regarded as
exhausting the subject of thermodynamics, to the point that the word "thermody-
namic" is sometimes used to mean "at equilibrium." This is too restrictive a
viewpoint.
which is the local form of the second law. If again the principle of local action
is accepted, the entropy density at a point, S, depends only on the state of a
neighborhood of that point, CT.
It is convenient to expand the second term on the right-hand side of equation
(1.6.2) to obtain
(1.6.4)
which yields directly some interesting conclusions. First, suppose the body con-
sidered is locally isothermal, say grad T = O. The isothermal local form of the
second law is
(1.6.5)
i.e., in steady heat conduction through a stationary body the heat flux vector
needs to have a positive component in the direction of decreasing temperatures.
We note, however, that this need not be universally true, not even if heat
conduction is the only phenomenon taking place, since the result has been
obtained by considering a steady-state process. (See Chapter 7 in this regard.)
Finally, the local rate of heating can be eliminated between equations (1.4.8)
and (1.6.5), yielding the following equation:
which forms the basis for a theory of dissipation to be discussed in the next section.
The customer cannot win at this game; this is the first law. In
fact, the customer is likely to lose; this is the second law.
(From the book of instructions for croupiers at the
roulette table.)
The local rate of energy dissipation per unit mass, Z, is simply defined as
and hence the second law assumes the following, very simple form:
Z~O (1.7.3)
It is noteworthy that the first three terms on the right-hand side of equation
(1.7.2) do not contain any heating term, and therefore their sum may be called
the nonthermal dissipation rate, ZM, i.e.,
ZM = TS· - U· + w (1.7A)
The last term is uniquely related to the conductive heat flux and is called the
thermal dissipation rate, ZT, i.e.,
Hence
(1.7.6)
A=U-TS (1.7.7)
26 We note that A is an extensive quantity which is a function of state.
Chapter One
Differentiation of equation (1.7.7) with respect to time yields
-A'-ST+w~O (1.7.9)
which shows that, in fact, elastic energy can be accumulated isothermally either
by an increase of internal energy, or by a decrease of entropy, or a combination
thereof. For certain classes of materials, the microscopic theory suggests that in
fact elastic energy is accumulated entirely by a decrease of entropy. Such materials
are said to have entropic elasticity.
The concept of entropic elasticity is not restricted to elastic materials, i.e.,
to materials which undergo only reversible processes. In fact, consider the
isothermal deformation of any material. The work done can be expressed as
i.e., as the sum of the rate of nonthermal dissipation and the rate of accumulation
of elastic energy; the latter can still be accommodated by the two mechanisms
discussed earlier.
(1.8.1)
Q,+P'E= 0 (1.8.3)
Some definitions are now needed. The external surface of the machine is
decomposed as follows:
(1.8.4)
where
>o
q. ds { <0 (1.8.5)
=0
28 The physical meaning is obvious. The three terms on the right-hand side of
Chapter One
equation (1.8.4) represent, respectively, that part of the external surface of the
engine through which heat flows into the machine by conduction, that through
which heat flows out, and the adiabatic part.
Analogously, the entire mass of the engine is decomposed in three parts
such that
(1.8.6)
(1.8.7)
and
Q- = - L- q • ds - L- Q dm (1.8.8)
which have an immediate physical meaning: Q+ is the rate of heat entering the
engine, and Q- is the rate of heat exiting the engine. By definition, both Q+ and
Q- are nonnegative, and
(1.8.9)
(1.8.10)
Before applying the second law, the following definitions are useful:
T+ = max(T) (1.8.11)
r = min(T) (1.8.12)
(The equality sign would only apply if all points at which heat is entering the
system were at temperature T+, and all points where it is exiting were at
temperature T-.)
Substitution of equations (1.8.1) and (1.8.14) into equation (1.5.1) yields the
following fundamental result, which is obtained solely from application of the
first and second laws to thermal engines:
(1.8.15)
(1.8.16)
(1.8.17)
(1.8.18)
(1.8.19)
(1.8.20)
The highest possible efficiency of a heat pump is always larger than unity.
Appendix
Examples
Pt = mUdU/dt = K; (1.E.3)
and hence W t = 0: there is no net work done on the elevator, which is consistent with the
fact that the elevator can be regarded as a rigid body. Hence the first law, in the form of
equation (l.4.2), reduces to
U;= Qt (I.E.4)
(with presumably both the right- and left-hand sides being zero).
Now suppose one wants to use the concept of potential energy. The potential energy
with respect to a horizontal plane located at h = 0 is Wh (with h measured upward), and
U = dh/ dt. Thus
</;= wu (I.E.S)
and thus the first law, in the form of equation (1.4.3), again reduces to equation (l.E.4).
The friction against the shafts, D, is of course a dissipative force. However, dissipation
does not take place in the elevator itself. To clarify this point suppose that, between the
elevator's slides and the shafts, there is a thin layer oflubricant. The surface of the lubricant
in contact with the slide is moving upward with velocity U; the surface in contact with
the shaft is stationary. The two surfaces are parallel to each other, and hence the layer of
lubricant is being sheared. Shearing is of course a deformation, which is possible since
the lubricant is quite obviously not a rigid body. The overall process is irreversible, since
dissipation of energy occurs in the lubricant layer at a rate DU; however, the process
which the elevator itself undergoes is nondissipative.
Problems
1.1. Consider those air conditioners which, in wintertime, are used as heaters. Suppose you
have to calculate the power required, assuming that the actual efficiency is close to the maximum
possible. Would you design based on the coldest day in winter or the hottest day in summer? Is the
answer to this problem going to be the same all over the US, or does it depend on geographical location ?
1.2. You may have seen those little toys shaped as birds which are pivoted on a horizontal
axis. The toy is started by tipping the bird's beak into a glass of water. After a while the bird straightens
up, stays in that position for several seconds, and then dips its beak into the water again; the trick
seems to go on forever. The toy works as follows. Water and air are at the same temperature; when
the beak temperature is the same, the equilibrium position is with the bird standing up, and that's
why the bird straightens out of the water. However, the beak is wet, and it cools down by evaporation
in the air; now the equilibrium position is with the beak down, and the bird moves again after enough
evaporation has taken place.
32 Since friction of the pivot axle is perhaps small but finite, there is energy dissipation. How does
the toy's going up and down apparently undefinitely square with the second law? You are only asked
Chapter One to give a qualitative explanation of the phenomenon.
1.3. Consult any book on refrigeration technique, and you will find a description of an
ammonia·based refrigeration cycle which only uses a heat source to drive it. Analyze such a cycle
and show that the upper limit to its efficiency is still given by equation (1.8.19).
1.4. When a heat pump is needed which pumps heat over a large temperature difference, it
may be impossible to realize it with anyone machine. In this case two machines are used: the first
one pumps heat from the cold source to some intermediate temperature, where it discharges it to the
cold side of the second machine; the latter pumps it up to the desired level.
Is the maximum possible overall efficiency of such a scheme equal to that which would hold in
the case of a single machine?
LITERATURE
The formulation of the second law as given in equation (1.5.6) is usually called the
Clausius-Duhem inequality. Admittedly, there is no general consensus on whether the
second law should be formulated in general as the Clausius-Duhem inequality; see, e.g.,
A. E. Green and P. M. Naghdi, Proc. R. Soc. London, Ser. A 357, 253 (1977).
However, the Clausius-Duhem inequality has been very fruitfully employed in' a
number of recent analyses. A discussion of its logical foundations can be found in M.
Feinberg and R. Lavine, "Foundations of the Clausius-Duhem inequality," Appendix
2-A, in: C. A. Truesdell, Rational Thermodynamics, 2nd ed., p. 123, Springer-Verlag, New
York (1984). This appendix also discusses the mathematical structure of thermodynamic
theories. The book including this appendix is a good source for the foundations of the
thermodynamic approach taken in this first part.
It is difficult to pinpoint exactly where the Clausius-Duhem inequality was first stated
explicitly; the best source is B. D. Coleman and W. Noll, Arch. Ratl. Mech. Anal. 13, 167
(1963).
Historically, the Clausius-Duhem inequality has developed as follows. The work of
Planck in 1887 implied that, in general, the second law could be written as dU :5 dw + T dS.
If the differentials are interpreted as rates, this corresponds to U":5 W + TS", which has
been called the Clausius-Planck inequality, and it corresponds to omitting the last term
on the left-hand side of equation (1.6.7) (or, equivalently, it corresponds to the requirement
that ZM is nonnegative). If temperature is uniform in space, the Clausius-Duhem and
Clausius-Planck inequalities are equivalent, but they are not if grad T is different from
zero. If equation (1.6.6) is assumed to be universally true (i.e., Zr is required to always
be nonnegative), then the Clausius-Duhem inequality implies the Clausius-Planck
inequality. The Clausius-Duhem inequality by itself requires the sum ZM + Zr to be
nonnegative, without requiring the two addends to be separately nonnegative.
There has been an argument in the literature as to whether the temperature scale
appearing in the denominator of equations (1.5.4) and (1.5.5) should be the same; see,
e.g., M. E. Gurtin and W. O. Williams, Z. Angew. Math. Phys. 17, 626 (1966).
A mild global assumption, however, has been shown to be sufficient to imply that 33
indeed the same temperature scale should be used; see M. E. Gurtin, Z. Angew. Math.
Phys. 27, 775 (1976). First and
There is general consensus on the formulation of the first law, although in most Second Laws
textbooks it is not expressed in terms of rates as we have chosen to do. The validity of
equation (1.3.8) for rigid-body motions is discussed in any standard textbook on the
mechanics of rigid bodies.
Thermal engines are discussed in detail in most textbooks of thermodynamics for
mechanical engineers. A less known type of thermal engine is the rubber engine, which
makes use of the properties of entropic elasticity exhibited by rubbers (see Sections 5.4
and 8.1). Rubber engines are discussed by R. J. Farris, Polym. Eng. Sci. 17, 737 (1977).
A procedure which turns out to be illuminating, but is nonetheless seldom followed,
is to read the classics. Carnot's work, Reflexions sur la Puissance Motrice du Feu, was
published by Bachelier in Paris, 1824; an English translation can be found in W. F. Magie
(ed.), The Second Law o/Thermodynamics, Harper and Brothers, London (1899). The first
Clausius paper on thermodynamics, "Ueber die bewegende Kraft der Warme, und die
Gesetzte, welche sich daraus fur die Warmelehre selbst ableissen lassen," is in Ann. Phys.
(3) 19,368, 500 (1856). This is cited by J. W. Gibbs in his obituary of Clausius, Proc. Am.
Acad., Vol. xvi, 458 (1889). Clausius published in 1897 a book, Theorie Mechanique de la
Chaleur, Monceaux, Bruxelles, where his thermodynamic work is summarized. So did
Joule in 1872, Das Mechanische Warmeaequivalent, F. Wieweg, Braunschwig; his original
paper, "On Matter, Living Force, and Heat," appeared in the Manchester and Lancashire
General Advertiser, May 5-12, 1847.
Berthelot's contributions are well discussed in his two books, Thermochimie and
Calorimetrie Chimique, published by Gauthier-Villars in Paris in 1897 and 1905, respec-
tively.
Duhem's technical work is summarized in his books Mechanique Chimique,
A. Hermann, Paris (1897) and Energetique, Gauthier-Villars, Paris (1911), and his phil-
osophical views on science in La Theorie Physique, M. Riviere, Paris (1914).
Finally;Gibbs's fundamental thermodynamic work is presented in Trans. Conn. Acad.
2, 309 (1873); 2, 382 (1873); 3, 108 (1876); 3, 343 (1878).
Chapter Two
NOTATION
Superscripts
* At equilibrium
Substantial time derivative
2.1. STATE AND SITE
In the preceding chapter, the mathematical nature of the state has been left totally
unspecified. Without such a specification, no results can be obtained in addition
to those given in the previous chapter. However, it should be borne in mind that,
when a specific mathematical structure is assigned to the state, the applicability
of the resulting theory is restricted to classes of materials and! or phenomena for
which the assigned state is a realistic one.
Referring back to the discussion on different conceptual levels of constitutive
assumptions in Section 1.1, in this chapter the second lower level is considered,
i.e., assumptions are made about which variables determine the state, but no
assumptions are made on the specific functional form ofthe constitutive mappings.
Furthermore, the somewhat unusual concept of site is introduced, as distinguished
from state. This point is discussed in detail below; suffice here to say that the
concept of site is essential in the distinction between equilibrium and nonequili-
brium properties.
One needs to begin by assigning as simple as possible a mathematical
structure to the state. It should be borne in mind that, by assigning the state a
very simple mathematical structure, the resulting theory will be comparatively
simple, but it will be applicable only to a restricted class of materials and! or
phenomena. More complex cases will need a more complex formulation, and
the resulting theory is more difficult. Fortunately enough, a nontrivial theory
which is applicable to a rather large variety of pragmatically relevant problems
can be formulated on the basis of an extremely simple mathematical structure
for the state.
A theory which allows for long-range interactions would be hopelessly
complex, and thus it is assumed that the principle of local action holds, i.e., that
the values of the densities of the extensive quantities which are functions of state
(such as the internal energy density U), as well as the local values of any intensive
function of state (such as pressure), are uniquely determined by the local state 37
38 CT. Therefore, all equations will be developed in the local form. Should the local
state be constant throughout the whole body considered, the value of the extensive
Chapter Two
properties, such as U" would simply be equal to the product of U times the
mass of the body. If CT is not constant throughout the body, equation (1.2.1)
should be used.
The first step in assigning mathematical structure to CT is to choose a set of
"state variables." The simplest possible set is as follows. As was discussed in
Chapter 1, a nontrivial thermodynamic theory requires that deformation of bodies
be taken into account. The simplest possible deformation of a body is a change
of density; hence density, or (as commonly done) its inverse, i.e., the specific
volume V, is chosen as one of the state variables. A nontrivial theory requires
also at least one nonmechanica1 state variable, and therefore temperature T is
also included. Both V and T are local quantities which may well not be constant
in space.
Quantities V and T are legitimate state variables, since their values can in
principle be measured by making measurements only on the body itself (for
instance, velocity would not be a legitimate state variable, since its measurement
is based on reference to some other body which is arbitrarily regarded as being
fixed). However, V and T enjoy a special property: their values can be imposed
at will, and independently of each other, at anyone time (proof of this statement
is rather involved, and will be omitted here). Such variables are called external.
State variables which cannot be imposed at will independently of the others,
which may certainly be significant for a variety of systems, are called internal.
It is now possible to define the site a. The concept of site is related to the
consideration of equilibrium, and is best understood by considering how an
equilibrium experiment is to be performed. Suppose, for instance, that we wish
to determine the equilibrium pressure exhibited by a substance. We would run
an experiment where we keep constant as many variables as we can, and measure
the resulting pressure; we would expect the measured pressure to reach, after a
sufficiently long time has elasped, a constant value, which we interpret as the
equilibrium pressure corresponding to the values of the variables which we have
held fixed. That set ofvalues is what will be called the site. Now only external
variables can be assigned at will, and hence only external variables can contribute
to determine the site. However, there is a subtlety involved here, and one needs
to define the site as the set of external state variables which can be held fixed at
any value one wishes and for how long one wishes. At first sight, that seems to
include all external state variables, but that is not the case. Indeed consider, e.g.,
the rate of change of volume, V·. Given a triplet V, T, V·, its value can be
assigned at will at anyone time, and thus V· is recognized as an external state
variable. However, the same triplet can be held constant in time only if V· is
zero, and thus V·, though being an external state variable, cannot be a member
of the set identified as the site. The question is that keeping the site constant in
time means that all the variables appearing in the site have to be imposed
independently of each other at all times, which is more restrictive a condition
than the one defining the external state variables, Le., that they can be imposed
independently of each other at anyone time-but not necessarily at all times.
The definition of site given above allows us immediately to define what we
mean by equilibrium: the condition which will be observed after the site has been
held constant (at whatever arbitrary value has been chosen) for a sufficiently long 39
time. It follows from this definition that all constitutive properties are, at e.quilibrium,
State and
junctions only of the site (an assumption is implicit here, i.e., that as the site is Equilibrium
held constant from some time onward, the conditions which will eventually be
observed are independent of what happened before the site was held constant).
However, it should be remembered that constitutive properties are defined also
for nonequilibrium conditions; and their values in general will be determined by
the state, not the site.
For the very simple system considered so far, the site is
a = {V, T} (1.1.1)
and thus all constitutive properties are, at least at equilibrium, unique functions
of volume and temperature. Under nonequilibrium conditions, they may have
different values, since the state may in general not·coincide with the site; assump-
tions need to be made about what the state may be. The simplest possible
assumption is that the state and the site coincide with each other:
u=a (2.1.2)
Systems for which equation (2.1.2) holds are called elastic. For elastic systems,
there is no room for a meaningful theory of equilibrium. In fact, any function
of state for an elastic system depends only on the site, and hence has the same
value independently of whether the site is being held constant (eqUilibrium) or
is changing in time.
A process lP(t) has already been defined as the function which maps time
into the local state:
u = 1P(t) (2.1.3)
a = lR(t) (2.lA)
Appendix
In this section, we have been somewhat cavalier about the question of which
transformations and which processes are admissible. The problems to be con-
sidered are as follows. First, we consider the case of transformations, and in
particular we consider the case where the site is as simple as in equations (2.1.1).
While it is certainly true that V values can be assigned at will at any given time
(it is only necessary to consider a cylinder equipped with a piston, which need
not be frictionless, to convince oneself that indeed one can assign V at will, given
40 arbitrarily large forces acting on the piston's shaft), there is a difficulty if one
wants to consider values of V which are discontinuous in time-so that V', may
Chapter Two
in fact be infinitely large. Values of V', approaching infinity would result in
conceptual problems in a viscous theory such as the one to be discussed in Section
2.3. Even more subtle conceptual problems arise if one considers the question
of which processes are to be regarded as admissible. These conceptual problems,
however, have no relevance to the analysis to be developed in the remainder of
this chapter.
Attention is still restricted to bodies for which the only relevant deformations
are changes in density, so that the only nonthermal state variable is V. This means
either that attention is restricted to materials on which it is possible to perform
a nonzero net mechanical work only by changing their density, or that attention
is restricted to phenomena where net work is done only by changing the density
although the material itself could absorb other types of net work should a wider
class of phenomena be considered.
At any point in a continuum body there may be internal stresses. Of these,
only the pressure p does any work in changes of density. Thus, within the
restrictions stated above, one may restrict attention to only pressure as far as
internal stresses are concerned. The instantaneous net rate of work per unit mass
done by pressure is given by
w = -pV' (2.2.1)
so that the local form of the first law becomes, for the case at hand,
p = f(u) (2.2.3)
v 41
State and
Equilibrium
Now consider the special case where equation (2.1.1) holds, say the site a
is simply the ordered pair V, T. A pure gas may be a reasonably concrete example
of this. Now consider two distinct transformations of such a system, 1R1 and R2 ;
see Figure 2.2.1. For both transformations T is constant, so that IRI is an isothermal
expansion and 1R2 is an isothermal compression.
At time t*, the value of V is the same in 1R1 and 1R2 • The following question
arises: Is the pressure also the same in both transformations at time t*? Such a
question is a physical one; in other words, we are asking whether a real system
will, or will not, exhibit the same pressure. If we do not care about describing
the fact that the two pressures may not be equal, we may proceed with an elastic
theory: If the system is elastic, the state at t* is the same in the two transformations,
and hence the pressure will be the same. However, if we wish to describe the
possibility that the pressure may not be the same, we have to allow for the
possibility that the state may not be the same at t* in the two transformations-i.e.,
we have to move up to a higher level of generality than an elastic theory makes
possible.
Physically, one would expect intuitively that pressure would be approxi-
mately the same provided both the expansion and the compression take place
slowly enough; if on the contrary they take place very rapidly, one would expect
the two pressures at t* not to coincide, and in fact the pressure being larger in
the compression than it is in the expansion. Furthermore, one would expect the
pressure difference to increase with increasing "viscosity" of the gas. As will be
shown later, these expectations can be shown to be deducible from the second law.
However, in order to do so one has to relax the assumption that the system
considered is elastic. As will be seen later, elastic systems do not allow any type
of irreversibility, and therefore the thermodynamic theory of elastic systems is
essentially a reversible theory.
Appendix
dF=T·ds (2.2.A.I)
42 The balance of linear momentum in the neighborhood of a point is
Chapter Two
<l>v· = <l>b + div T (2.2.A.2)
where b is the field acceleration of the body force (usually gravity). Taking the
scalar product of equation (2.2.A.2) with the velocity vector v one obtains
On subtracting equations (2.2.A.3) from (2.2.A.4), one obtains the net rate
of work per unit volume:
wi V = T:grad v (2.2.A.S)
where the: sign indicates the scalar product of two tensors. We note that the
body forces do not contribute to the net rate of work.
When the only internal stress is an isotropic pressure, then
T= -p1 (2.2.A.6)
The concept of an elastic system can easily be generalized to the case where
there are more than one external state variable to consider in addition to tem-
perature; for instance, in an elastic solid the strain at any given point is a
three-dimensional tensor. Let the site be the pair Y, T, where Y is an n-dimensional
vector called the generalized volume. Correspondingly, there will be an n-
dimensional vector Q, called the generalized pressure, such that the net rate of
work at a point is given by
w = -Q·Y· (2.2.A.9)
The system is elastic if the state is also the ordered pair Y, T, and such a
system can only undergo reversible processes.
2.3. VISCOSITY AND RELAXATION 43
State and
One does not insist often enough on the fact that the use of Equilibrium
partial derivatives of thermodynamic functions is based on the
(albeit implicit) assumption that such functions are defined also
for non-equilibrium states. Indeed, it is often impossible within
the set of equilibrium states to change one variable while
keeping the other ones constant. When a partial derivative
implies consideration of non-equilibrium states, its
experimental determination may be difficult, but, nevertheless,
it is a powerful conceptual tool.
R. Defay and I. Prigogine
In view of equation (2.2.3), this implies that the state is the ordered triplet
V, T, V':
u = v, T, V' (2.3.2)
However, V' cannot be included in the definition of the site, for the reasons
discussed in Section 2.1. It therefore follows that a system for which equation
(2.3.1) holds is not elastic, since state and site do not coincide; in particular, the
site is still given by equation (2.1.1), while the state also includes the rate of
change of one of the state variables. Systems for which the state is determined
also by the rate of change of some or all of the external state variables are called
viscous.
On the basis of the definition of equilibrium given in the previous section,
it is obvious that a viscous system is at equilibrium when the rate of change of
the external state variables is zero. For the system considered here, eqUilibrium
corresponds to V· = O. Correspondingly, an eqUilibrium pressure p* (equilibrium
values will always be identified with an asterisk) is defined as
p* =f(V, T,O) =J*(v, T) (2.3.3)
We note that the equilibrium fuctionf*( . ) maps the site into the equilibrium
pressure. By definition, the eqUilibrium values of the functions of state depend
only on the site.
If one assumes that f( . ) is Taylor-series expandable at V· = 0, one can write
p = p* - BV', (2.3.5)
44 where B is minus the partial derivative appearing in equation (2.3.4). Since one
expects pressure to be lower in expansion, B is expected to be positive.
Chapter Two
We now consider the isothermal transformation shown in Figure 2.3.1. The
final site at t> t\ coincides with the initial site at t < to. Both before to and after
t\ the system is at equilibrium, but it is not in the time interval from to to t\. The
total network done in that time interval is (all integrals in this section are intended
as definite integrals over the whole transformation)
w= - f f( V, T) V' dt = - f f( V, T) dV = 0 (2.3.7)
The physical meaning is that an elastic system does as much work on the
surroundings during the expansion part of the transformation as it absorbs during
the compression part: the mechanical behavior of an elastic system is entirely
reversible.
Conversely, if equation (2.3.5) holds true, the total net work is
and although the final site coincides with the initial one a finite net work has
been done, and in fact a positive one if as expected B > O.
In viscous systems, only the instantaneous rate of change of the external
state variables affects the state: one could say that the external state variables'
values need to be known only at, and immediately before, the actual instant of
observation. In fact, there are materials (notably polymers) which have rather
long relaxation times, so that also the values at instants in time significantly
remote from the instant of observation affect the state. Such systems are called
relaxationaL The thermodynamic theory of relaxational systems is quite complex,
and only the essential features of it will be discussed in Chapter 5.
~
,,
,
'''
' I '
,, '''
,, '
,
I,
I
''
I'
,, ''
,, I' FIGURE 2.3.1. An isothermal transformation
t, with the final volume equal to the initial volume.
Viscous systems allow irreversible processes: for the transformation in Figure 45
2.3.1, the total net work done is dissipated, since the system at the end of the State and
transformation is in the same state as at the beginning. Also, viscous systems Equilibrium
allow a meaningful distinction to be made between equilibrium and nonequili-
brium values of the quantities of interest. However, the type of irreversibility and
of equilibrium considered in this section are not the only possible ones, and in
fact in the field of chemical engineering the pragmatically more important ones
are those which arise in systems with internal state variables.
Appendix
(2.3.A.l)
where D is the symmetric part of the velocity gradient tensor, IL is the shear
viscosity, and ILl is the bulk viscosity. Fluids obeying equation (2.3.A.l) are said
to be Newtonian fluids. If the only deformation is compression (or expansion),
D is given by
(2.3.A.4)
The Stokes hypothesis is just that, a hypothesis, and it need not necessarily
hold true-neither does, for that matter, equation (2.3.A.1) necessarily hold true.
If equation (2.3.A.1) holds, the constant B in equation (2.3.5) is, in fact, identified
with
(2.3.A.5)
w-A·-ST"~O (1.4.1)
Since both A and S are functions of state, for a viscous system described 47
by equation (2.3.1) two mappings a(·) and s(·) exist such that State and
Equilibrium
A = a(V, T, V·) (2.4.2)
and
S = s( V, T, V·) (2.4.3)
It may be worth noting that, since the mapping a(·) is uniquely identified
by equation (2.4.2), the partial derivatives appearing in equation (2.4.4) are
unequivocal: for instance, aaj a V is the partial derivative of the Helmholtz free
energy density with respect to volume when temperature and rate of change of
volume are held constant. In most books on thermodynamics, partial derivatives
are always written with subscripts identifying the quantities being held constant.
This is due to the fact that the same symbol is used for a mapping and for its
value; since different mappings may have the same value, a partial derivative
without subscripts would be equivocal. This point will be further clarified in the
section on baric derivatives.
Equation (2.4.4) must hold true for every conceivable transformation, say
for any conceivable set of values V, T, T", V', and V". (Since V and Tare
external state variables, their values, as well as the values of all their time
derivatives, can in principle be assigned at will at anyone instant of time-though
not at all times, of course.) As shown below, this requirement implies that the
constitutive mappings are not independent of each other. The second law imposes
restrictions on the form of the constitutive mappings, not on conceivable transfor-
mations.
Suppose that, at some particular instant in time, V, V', T, and T" have been
assigned, so that the value of every term in equation (2.4.4) is assigned, except
V". Since equation (2.4.4) must hold for arbitrary values of V", no matter what
their sign or magnitude, the only possibility is for the coefficient of V·· to be zero:
aajav'=o (2.4.5)
Equation (2.4.5) should not be understood to imply that the Helmholtz free
energy density depends only on the site in general; in fact, for many systems it
does not. Equation (2.4.5) implies that, if the state is indeed the ordered triplet
V, T, V', then A does not depend on V'.
The second law is now collapsed to
s = -aa/aT (2.4.7)
It should be noted that equations (2.4.5) and (2.4.8) are restrictions imposed
on the constitutive mappings a( . ) and s( . ), while equation (2.4.7) is a relationship
between these two mappings: Once a(·) has been assigned, the form of s(·) is
determined-but not vice versa. This is worded by saying that the Helmholtz free
energy is a potential for entropy.
The second law has now collapsed to
[aa/av + ply· s 0 (2.4.9)
We note, however, that now the same argument cannot be duplicated, because
when V· is changed, so is p, and one thus cannot fix the value of the square
bracket and yet allow for arbitrary values of V·. Now suppose that V and T
have been assigned. Equation (2.4.9) implies that
i.e., the Helmholtz free energy is also potential for the eqUilibrium pressure.
aa .p
av
fixed Y and T
Y·
In the preceding section, it has been seen that a crucial role is played by
the fact that T and V are external state variables. The fact that their values, as
well as the values of their time derivatives, can be assigned at will and indepen.
dently is crucial to the logic of deducing consequences of the second law. The
50 type of irreversibility discussed in the preceding section is somewhat special,
since it can be made as small as one wishes by having sufficiently slow transforma-
Chapter Two
tions.
In this section, internal systems are considered. A simple concrete example
is obtained by considering a chemically reacting mixture in a variable volume
box. While volume and temperature can be imposed arbitrarily and independently
of each other, the reaction goes on at a rate determined by its intrinsic kinetics,
and therefore the composition of the gas cannot be assigned at will and indepen-
dently. Given an initial composition, the composition at any subsequent time is
identified by one single scalar parameter, the degree of advancement of the
reaction, x. The quantity x is the internal state variable, and hence the simplest
structure for the state is
u={V,T,x} (2.5.1)
A = a(V, T, x) (2.5.2)
S=s(V,T,x) (2.S.3)
P = f(V, T, x) (2.5.4)
In addition, one needs an equation for the rate of change of the internal state
variable, x·, say for the concrete example one would need to know the kinetics
of the chemical reaction. Indeed, for all internal systems the rate of 'change of
the internal state variables must itself be a function of state: x being internal, its
value cannot be imposed from outside, and hence at anyone time it will change
at a rate governed internally, i.e., at a rate which is a function of state. For the
case at hand
x·=r(v,T,x) (2.5.5)
If one performs the same algebra as that leading to equation (2.4.4), one
obtains
One can now perform the same analysis as for equation (2.4.4) to obtain
the following results:
p = -aa/av (2.5.7)
S = -aa/aT (2.5.8)
Z = -(aa/ax)x· 2: 0 (2.5.9)
The Helmholtz free energy is again a potential for both pressure and entropy, 51
but the second law will in general be fulfilled as an inequality, say the dissipation
State and
rate Z will in general be positive. In fact, except at equilibrium, given a state V, EqUilibrium
T, x, neither aa/ax nor x' will be zero. Furthermore, while the dissipation rate
due to viscosity can be made as small as one wishes by imposing a sufficiently
small value of V', the magnitude of Z as given by equation (2.5.9) cannot be
controlled, since x' is not controllable. In particular, when chemical reactions
occur, energy is dissipated. [There is an important exception to this statement,
namely, reactions taking place in an electrochemical cell, where the reaction rate
depends also on the imposed electrical potential difference, which is an external
state variable.]
The above considerations deserve some additional comment. Suppose that
a viscous gas is brought isothermally from some initial volume VI to some final
volume V2 • The total dissipation during the transformation is given by
f Z dt =B f V 2 dt (2.5.10)
x* = K[V, T] (2.5.12)
We note also that, if V and T are held constant, equations (2.5.6) and (2.5.9)
imply that A can never increase; since A' is zero at an eqUilibrium point, the
value of A at an equilibrium state is the minimum compatible with the assigned
values of V and T. The theory of equilibrium for internal systems is essentially
concerned with the location of the equilibrium functions from the requirement
that free energy is minimized.
52 Now consider an internal system in a nonequilibrium condition, so that x
is different from x*. If the site is held constant, x will change in time at whatever
Chapter Two
rate is implied by equation (2.5.5) for such a condition; hence, the state will
change in time, and possibly quite slowly, so that it may take quite some time
before equilibrium is reached. It is now obvious why our definition of equilibrium
was the condition observed after the site has been held constant in time for a
sufficiently long time. In a viscous system, equilibrium is reached instantaneously
as soon as the site starts being held constant; that is not the case for internal
systems. In some cases, the rate of evolution toward equilibrium may be so slow
that, to all practical purposes, one could say that nothing changes in time, and
yet the system is not at equilibrium.
"The round square does not exist" had always been a difficult
proposition; for it was natural to ask "What is it that does not
exist?" and any possible answer had seemed to imply that, in
some sense, there is such an object as the round square, though
this object has the odd-property of not existing.
B. Russell
H= U+pV (2.6.1)
and
G=H-TS=A+pV (2.6.2)
H=h(V,T,x) (2.6.4)
G = g(V, T, x) (2.6.5)
The mappings are not independent, and in fact the free-energy one is a
potential for all the functions of state except x·. Equations (2.5.7) and (2.5.8)
give s( . ) and f( . ) directly as derivatives of a( . ), 'while from the definitions one
obtains immediately
u(·) = a(·) - T iJa/iJT (2.6.6)
(2.6.9)
and therefore the two baric derivatives (i.e., within the stated restrictions, partial
derivatives at constant pressure) are as follows:
and
131/13x = ai/ax - (al/aV)(af/ax)/(a//av) (2.6.13)
dp = (a//aY) dV (2.6.15)
dL = (alIa V) dV (2.6.16)
Therefore 55
State and
fJl/fJp = (al/aY)/(aj/aV) (2.6.17) Equilibrium
and will in general be differential, since p, S, and 8 have finite values. The
assumptions of invertibility for the constitutive functions imply that, for the same
differential change of state, the changes of all other functions of state will also
be differentials. One can therefore simply substitute the definitions to obtain the
following three additional equations:
dO = V dp - S dT + 8 dx (2.7.4)
and (2.7.5)
are derivatives of the functions mapping {H, p, x} into G and {T, p, x} into U.
Since the most common case is where one wants to regard {p, T, x} as the
state, we can simplfy the notation by using subscripts only in those few cases
where triplets other than either {V, T, x} or {p, T, x} are intended. We can also
drop the distinction between the symbol identifying a thermodynamic quantity
and the one identifying its constitutive mapping.
Relationships between partial derivatives can be obtained from the Maxwell
relations by a variety of shortcut methods. Some of thesee are discussed below.
Hence
Two partial derivatives playa very important role and are therefore assigned
a special symbol: the "specific heat at constant volume," cv, and the "specific
heat at constant pressure," Cp,
Cv = aU/aT (2.7.11)
Cp = 8H/8T (2.7.12)
Appendix
and the coefficients M and N were called the latent and the sensible heat capacity.
The coefficient N is immediately recognized as the constant volume specific heat.
Substitution of the first law in the form of equation (2.2.2) yields
N=p+aUfaV (2.7.A.2)
which guarantees that the heating rate is zero. A little algebra with the Maxwell
relations shows that
p+au/av= Tap/aT (2.7.A.5)
which guarantees that p'/T' has the same sign as ap/aT. Thus in the region of
anomalous behavior of water the rates of change of pressure and temperature
have opposite signs, and this can be shown to result in major anomalies of Carnot
cycles.
Of all such scales, only one may be such that equations (1.5.4) and (1.5.5)
hold true, namely, the absolute temperature scale. The fact that this absolute
scale happens to coincide with the scale obtained by using an ideal-gas ther-
mometer is largely coincidental, and it has been both helpful in the development
of thermodynamic theory, and a stumbling block to it, as discussed below.
The concept of an absolute temperature scale was introduced by Lord Kelvin 59
in 1852. His argument was essentially as follows. Consider a substance which
State and
undergoes a differential change of state dV, dT. The argument happens to be Equilibrium
correct even if the state has more structure than being simply the ordered pair
V, T, provided the following conditions are satisfied: (1) all other external state
variables are being held constant, (2) there are no internal state variables, and
(3) work can in fact be expressed by equation (2.2.1). If an absolute temperature
scale has not yet been established, the change of state has to be identified by dV,
d~, ~ being whatever arbitrary temperature scale has been chosen. The work
done on the surroundings is p dV, and the amount of heat received by the
surrounding is
dq = N d{3 +M dV (2.8.2)
where N and M were called the sensible anq latent specific heats. In modem
terminology, the quantities Nand M are identified with
and
M = p + (iJU/OV)fj = p + (iJU/iJVh (2.8.4)
(2.8.6)
where F(f3) is a function which is the same for all substances. The absoJute
temperature scale was thus established as being T = F(f3). Indeed, if f3 is
identified with T, equation (2.8.7) becomes, in modern terminology,
which is of course equation (2.7.10). As was discussed before, the fact that T
happens to coincide with the temperature measured by an ideal gas thermometer
made matters somewhat easier for the pioneers; however, in an ideal gas au/ aV
is zero, and hence the distinction between the quantity M and pressure itself was
a subtle one to identify.
Happy is the man that findeth wisdom, and the man that
getteth understanding.
For the merchandise of it is better than the merchandise of
silver, and the gain thereof than fine gold.
Proverbs 3, 13-14
The distinction between site and state may, at first sight, look both artificial
and somewhat obscure; it is useful to return to this point after having discussed
some of the implications. It is easiest to discuss the matter by considering a
simple reacting mixture, for which the only difference between site and state is
that the former is the ordered pair V, T, but the latter includes an internal state
variable x; however, all the points made below are more generally applicable.
The site is the set of those variables which (1) can be held constant at any
value one may wish (which is what is done in an equilibrium experiment), and
(b) are tentatively supposed to be the only ones which matter in determining the
equilibrium behavior. The pair V, T satisfies condition (1), but is not guaranteed
to satisfy condition (2), as the following two simple counterexamples show.
Let us consider an elastic spring. It is clearly possible to extend the spring,
without changing either its volume or its temperature. However, if one measures
the force needed to keep the spring elongated at some length I, which is obviously
a function of state, one reaches the conclusion that it is not constant when V
and T are held constant, but its value depends on 1 as well. One can now ask
oneself whether it is possible to keep 1 constant independently at any preassigned
value while keeping V and T constant as well; the answer is obviously yes. For
this system, one thus comes to the conclusion that the site is not simply the
ordered pair V; T, but it must be extended to at least the ordered triplet V; T, I; 61
correspondingly, a new function of state needs to be considered, i.e., the axial State and
force acting on the spring. The latter will eventually attain an equilibrium value Equilibrium
which depends only on the site when the latter is held constant for a sufficiently
long time, but of course there is no guarantee that it will do so instantly as soon
as the site starts being held constant-there may well be some delay.
Another useful example is that of an electrochemical cell, like the battery
of an automobile. One can certainly maintain constant V and T and yet measure
a response which depends on how the external circuit is set: if current is drawn
from the battery, the electrical potential difference measurable between the two
electrodes will not be the same as that measurable while the battery is being
recharged. One thus concludes that it is necessary to regard the applied electrical
potential as an additional variable which determines the site. The thermodynamic
theory of electrochemical cells will be discussed in a later chapter; here the
example is brought forward only as further confirmation of the fact that the pair
V; T need not be the site in all conceivable cases.
Turning attention back to the case of a reacting mixture, the state is the
triplet V; T, x. It is quite obvious that is is possible for the system to be in an
infinite variety of states at any given value of the site-x is a measure of the
composition of the system, and certainly at any given value of the pair V; T
infinitely many different compositions are possible. The reason that x is recognized
as an internal state variable (in contrast to the length of the spring in the first
example above) is that there is no way of keeping x constant at some arbitrary
preassigned value while keeping V and T independently constant as well. It is
also evident that, should one keep V and T constant, x will change in time-the
system is at a constant site, but its state is changing in time. Sometimes the rate
of change will be extremely slow, in fact so slow as to be unmeasurable, and one
could (wrongly) conclude from an experiment that the system is at equilibrium.
For instance, in a mixture of carbon monoxide and oxygen at room temperature
and pressure the rate of oxidation will be unmeasurably small, and so for all
practical purposes x will in fact be constant in time; yet the system is not at
equilibrium. If one fires a spark in such a mixture, the combustion reaction will
in fact proceed to chemical equilibrium, and if the heat of reaction is removed
the system will at the end be at the same volume and temperature, but at a
different composition-there will be quite a bit of carbon dioxide in it, the total
number of moles will be less than it was before, and the pressure will be
correspondingly lower. Unreacted mixtures are not the only example of apparent
equilibria: the glassy state, for instance, is not an equilibrium state, yet its evolution
toward the crystallized equilibrium state is extemely slow and often so slow as
to be unobservable.
It is important to realize that, while all functions of state have equilibrium
values which depend only on the site, there is a distinction between site and
equilibrium state. Again consider the example of a reacting mixture, with the site
being V; T and the state being V; T, x. If the reaction is allowed to proceed until
chemical equilibrium is reached, x will have a value x* which depends uniquely
on the site. The equilibrium state is the triplet V; T, x*, which is uniquely
determined by the site V; T, but does not coincide with it. The statement that
such a system is in an equilibrium state implies that x has indeed the value x*;
62 the statement that the same system is at some site V, T has no such implication-
x may well be different from x* at such a site and, as was discussed in the previous
Chapter Two
paragraph, may in fact stay different from x* for very long stretches of time.
Another conceptual issue which is worth some discussion is the following
one. In mechanics, it is possible to develop a logically coherent theory of statics
without ever appealing to dynamics; this is related to the fact that one can write
down the two basic laws of mechanics directly for the static subcase (the sum
of all forces acting on a system, as well as the sum of all torques acting on it, is
zero). This is not the case in thermodynamics, since there is no satisfactory way
of writing the second law (and perhaps not even the first one) as valid for the
static (or equilibrium) case. In most books on thermodynamics, the "equilibrium"
form of the second law is written down as
dS = dq/T (2.9.1)
but the question which arises is, of course, what one means by dS and by dq. As
far as dS is concerned, one could say that it is the difference between the entropies
at two neighboring states; this only introduces the logical difficulty of what one
means by two equilibrium states being close to each other, but perhaps that could
be circumvented. However, what is dq? The standard answer is that it is the heat
absorbed in a reversible transformation leading from the first to the second state;
however, apart from the difficulty of establishing what is meant by a reversible
transformation without touching on the question of what is meant by an irrevers-
ible one (as would be required if a purely static theory has to be developed),
this answer introduces the concept of a transformation-and, by definition, at
equilibrium no transformation occurs.
Often this point is circumvented by bringing in another difficult concept,
that of a quasi-static transformation, which proceeds "through a sequence of
equilibrium states." Quasi-static is an impressive word, but the only meaning
which can be attached to it is the less impressive word "slow"-and how can
one speak of slowness without implying the concept of time? How slow is slow
enough? If one chooses to develop a thermodynamic theory (rather than a
thermostatic one), the answer is easy. For instance, in the case of a system where
the state is V, T, V·, one needs to assume thatf( ) is a Taylor-series expandable
at V· = 0 to obtain equation (2.3.4). One then reaches the conclusion that if the
condition
1. Consider a spring which, under the influence of a tensile force f. can be brought
to some length I other than its rest state length. The length of the spring may vary without
any change of volume. One thus comes to the conclusion that there are in fact at least
three external variables which can be imposed arbitrarily and independently of each other:
V, T, and I. We therefore identify the site as ex = {V, T, I}. Correspondingly, there are two
mechanical functions of state, i.e., pressure p and tensile force f. and the rate of work is
-pV·+ fl".
First consider the case where the system is elastic, i.e., the state is u = {V, T, I}.
Equation (2.4.1) yields
Since the three rates can be imposed arbitrarily without affecting the values of the
three brackets, one concludes that free energy is a potential not only for pressure and
entropy but also for the tensile force
f = aAjal (2.E.2)
2. Since the state is V, T, I, in general the internal energy U will depend on the
length of the spring, I. However, in the case of a spring made of rubber it turns out that
in fact internal energy is independent of I. This can be ascertained experimentally as
follows. First, the constant volume specific heat is determined experimentally; for simplicity
assume that Cy is independent of temperature. Next, the spring is elongated adiabatically,
and the temperature rise of the spring (if any) is measured. Suppose that U = u( V, T).
Since the spring has been elongated adiabatically, the work done, W (which can be
measured), must be equal to the increase of internal energy. Since V has not been changed
by the elongation, U can only increase if temperature increases. The temperature increase
must be equal to W j Cy, and this can be checked experimentally. For rubbers, the agreement
is quite satisfactory, and one concludes that indeed U = u( V, T). In view of equation
(2.E.2), and of the fact that aU jal = 0, one thus concludes that
f= -TaSjal (2.E.3)
-s=aujaT-S-TaSjaT (2.E.4)
and hence
Tas/aT=au/aT (2.E.5)
and
a2 SjaTal=0 (2.E.6)
This guarantees that aSj al is independent of T, and hence that the force f is proportional
to absolute temperature. The elastic moduli of rubbers are indeed proportional to absolute
temperature.
64 3. Now consider a spring as in the first example, but allow for the possibility of
viscous effects-i.e., that the tensile force required to elongate the spring is different from
Chapter Two the tensile force that the spring exhibits during unloading. This can be described by
assuming that the state is u = {V, T, ~ n.
Thus the second law becomes
First, since 1- can be imposed arbitrarily, one concludes that free energy is in fact"
independent of the rate of elongation, so that the last term on the right drops out. The
rates of change of temperature and volume can now still be imposed arbitrarily without
changing the values of the brackets in equation (2.E.7), but the rate of change of length
cannot, since it contributes to the determination of the state. Thus one concludes that free
energy is a potential for pressure and entropy, but not for the tensile force. The second
low reduces to
(f - iiA/iil}l" 2: 0 (2.E.8)
This restricts the values of (f - iiA/iJI), if plotted at constant Ivs. r, to the even
quadrants, and thus, provided!(l") is sufficiently well behaved near r = 0, one concludes
that
Equation (2.E.S) now requires the tensile force in loading to be larger, and that during
unloading to be smaller than the equilibrium value corresponding to r = o.
Problems
2.1. Suppose that, for some fluid system, it has been determined experimentally that the pressure
in isothermal expansion is given by an equation of the form
p = p*-Aff (2.P.I)
LITERATURE
The concept of "site," as used in this chapter, was introduced in G. Astarita and
G. C. Sarti, Chim. Ind. (Milan) 57, 680, 749 (1975).
The technique of deriving consequences of the Clausius-Duhem inequality used in
this chapter makes crucial use of the concept that external state variables, as well as their
time derivatives, can be imposed arbitrarily and independently of each other. A formal
proof of this is presented in G. Astarita, An Introduction to Nonlinear Continuum Thermody-
namics, SpA Editrice di Chi mica, Milan (1975).
The question of the constant pressure specific heat at phase transitions is discussed
in more detail in Section 4.5.
The question of admissibility of processes and transformations, discussed in the
Appendix to Section 2.1, is conceptually very important. See in this regard the paper by
Feinberg and Levine cited in the Literature section of Chapter 1.
Dissipation in a Maxwellian gas, and the lack of it in pure expansions and compress-
ions, is discussed in detail in the following two references: H. Grad, "Principles of the
Kinetic Theory of Gases," in Encyclopaedia of Physics, Vol. XII, pp. 205-294, Springer-
Verlag, Berlin (1958); c. A. Truesdell, Rational Thermodynamics, 2nd ed., Chapters 8, 9,
and 10, Springer-Verlag, Berlin (1984).
The concept of an absolute temperature is one which has a long tradition and a very
rich literature. Possibly the best recent discussion of the subject, which includes a historical
perspective, is M. Pitteri, in: C. A. Truesdell, Rational Thermodynamics, 2nd ed., Appendix
G6, Springer-Verlag, Berlin (1984).
We have used the idea that entropy is a perfectly legitimate concept also when the
system considered is not at equilibrium. This is always a moot point, but the reader is
simply asked to consider a mixture of hydrogen and oxygen at ambient conditions, a
system for which nobody would deny an entropy is a perfectly acceptable concept, and
yet the system is not at equilibrium, since water would be present at equilibrium in
such a quantity as to make the concentration of either oxygen or hydrogen negligibly
small. That entropy is a perfectly legitimate concept in nonequilibrium situations was so
obvious to the pioneers that they didn't feel the need to make the point explicitly: the
only one who made the point explicitly was J. W. Gibbs, "Graphical methods in the
thermodynamics of fluids," Trans. Conn. Acad. 2, 309 (1873).
The question of invertibility of the constitutive mappings is delicate. If one considers
the mapping delivering the entropy, s( V, T), this is invariably invertible for temperature
(even in highly more complex cases), and hence entropy, rather than temperature, could
be used as an independent variable; this has, e.g., to do with the speed of sound, to be
discussed in Chapter 8. Should one use the pair V, S as the state, temperature can easily
be shown to be (aU/aS)v, which of course guarantees that the derivative (au/aS)v exists
and is always positive. Indeed, Truesdell and Toupin, The Classical Field Theories, Springer-
Verlag, Berlin (1960), develop the classical thermodynamic theory by requiring that internal
energy depends, in addition to mechanical variables such as V, on another variable S
which is dimensionally independent of the mechanical variables; the latter is then identified
66 with entropy. In the mechanical engineering literature, often the pair S, T is used as the
state; this implies, albeit implicitly, that the mapping s( V, T) is invertible for volume,
Chapter Two which is almost always, but not invariably, true. In fact, at constant T, S is generally an
increasing function of V; however, for instance, when ice melts S increases and so does
1/ V-a very simple counterexample.
The question of invertibility of the f( ) function with respect to temperature, which
has been discussed in the Appendix to Section 2.7, casts doubt on the significance of the
axiomatic approach of C. Caratheodory, Math. Ann. 67, 355 (1909), who regards the pair
V, p (or generalizations thereof) as identifying the state. Other difficulties with
Caratheodory's approach have been discussed by G. Whapples, 1. Ratl Mech. Anal I,
302 (1952); B. Bernstein, 1. Math. Phys. 1,222 (1960); J. B. Boyling, Proc. R. Soc. London
Ser. A 329, 35 (1972); J. L. B. Cooper, 1. Math. Anal Appll7, 172 (1967).
The related problem of the anomalies in Carnot cycles resulting from adiabates along
which the rates of change of pressure and temperature have different signs is discussed
by C. Truesdell and S. Bharatha, The Concepts and Logic of Classical Thermodynamics as
a Theory of Heat Engines, Springer-Verlag, Berlin (1977), and by J. S. Thomson and T. J.
Hartka, Am. 1. Phys. 30, 26, 388 (1962).
The concepts of affinity and of "extent of reaction" were first put forward by De
Donder and van Rysselberghe, Thermodynamic Theory of Affinity, Stanford University
Press (1936).
A purely thermostatic theory, which is strictly constrained to equilibrium values of
all functions of state, has in fact been developed by J. W. Gibbs within the restricting
assumption that the state is V, S: Trans. Conn. Acad. 3-16, 108,343 (1876).
Chapter Three
HOMOGENEOUS REACTIONS
NOTATION
B Any component
B( ) Component distribution
c( ) Concentration distribution kmolm- 3
D( ) Difference operator
E Electrical potential between electrodes volt
E' Applied electrical potential volt
F Faraday's constant coulomb/ equiv
f( ) Constitutive function for pressure atm
g( ) Constitutive function for free enthalpy kcal kmol- I
G{ } Constitutive functional for G
G'{ } Functional derivative of G{ }
h Displacement from equilibrium kmolm- 3
I Current intensity ampere
k( Kinetic constant distribution function S-I
Subscripts
j Componentj
k Reaction k
p Atomp
Total
0 Initial
Superscripts
* At equilibrium
f For formation reaction
Substantial time derivative
0 At standard state
3.1. A REVIEW OF STOICHIOMETRY
(3.1.1)
Equation (3.1.1) does not, of course, imply addition in the ordinary algebraic
sense of the quantities CO and O2 • The meaning of equation (3.1.1) is to recall
the experimentally observed fact that, when a given number of moles of CO is
consumed by the reaction, the same number of moles of CO 2 is produced, and
half as many moles of O 2 are consumed. Let the components appearing in the
reaction be numbered consecutively, say CO is Bt. O2 is B2 , and CO 2 is B 3 , and
let Uj be the corresponding stoichiometric coefficients, say UJ = -1, U2 = -!, and
U3 = 1. We note that the stoichiometric coefficients of the species appearing on
the left-hand side (the "reactants") are assigned negative stoichiometric
coefficients. Equation (3.1.1) can now be written as follows:
(3.1.2)
(3.1.3)
where x· is the rate of reaction. We note that the meaning in equation (3.1.3) is
left unchanged if all the stoichiometric coefficients are multiplied by the same
nonzero scalar. In particular, considering the case where the scalar is -1, one
sees that the distinction between reactants and products is arbitrary.
The set of stoichiometric coefficients of a reaction is subject to the restriction
of the fundamental axiom of chemistry, the permanence of atoms. In the specific 71
72 case of reaction (3.1.1), the atoms involved are carbon, C, and oxygen, O. The
symbols CO, O 2 , and CO2 are the brute chemiciu formulas of the three components
Chapter Three
involved. The subscripts represent the number of atoms in the component, with
no subscript being interpreted as a subscript of 1, and the absence of an atomic
symbol being interpreted as a subscript of zero. Let 1jp be the subscript of the
pth atom in the brute chemical formula ofthejth component. For reaction (3.1.1),
the matrix 1jp has the following form:
x
CO
C
1
0
J
All others
0
CO2 1 2 0
O2 0 2 0
Note that, for a component which is the molecule of one of the elements
(in this case, O2 ), the corresponding row has only one nonzero entry. That entry
will be identified by Tp , the number of atoms in the molecule of the pth element.
The axiom of permanence of atoms can be written in the form
(3.1.4)
t = 0, (3.1.5)
x= J: x· dt (3.1.6)
(3.1.7)
This latter equation deserves some comment. Given a system with N com-
ponents participating in the reaction, the composition space has N - 1
dimensions. In fact, since the total mass is fixed, the composition is identified
by the N mol fractions, only N - 1 of which are independent, since they must
add up to unity. For the special case of reaction (3.1.1), three components are
involved and hence the composition space is two-dimensional: the usual triangular
diagram could be used to represent possible compositions (see Figure 3.1.1). 73
However, equation (3.1.7) shows that only one parameter, X, is needed to describe Homogeneous
all compositions which can be reached from the initial one through the occurrence Reactions
of the chemical reaction, and hence the reaction subspace is one-dimensional.
For example, in the case of reaction (3.1.1), if the CO to 02 number of moles
ratio is 2 to 1 at any given time, it will stay at that value at all times; the reaction
subspace would be the straight line going through the CO2 corner.
For a system where only one chemical reaction may take place, i.e., a system
with a one-dimensional reaction subspace, the composition space would also be
one-dimensional only if the number of components were 2. This would require
the chemical reaction to be an isomerization, for which there is only one reactant
and only one product.
We now consider a system where more than one chemical reaction can take
place:
(3.18)
where Xk is the extent of the kth reaction. The XkS are internal state variables,
reaction
subspace
Appendix
(3.1.A.l)
for the M unknowns x~ has only the trivial solution x~ = O. Should the rank be
less than M, nontrivial solutions would exist. Let x~ be such a nontrivial solution.
One would have
(3.1.A.l)
and hence equation (3.1.9) would not determine the values of the extents of
reaction univocally. This shows how reduction to a set of independent reactions
is necessary for the theory of chemical equilibrium to be developed.
The question of the axiom of permanence of atoms being stronger than the
mass conservation requirement is as follows. The molecular weight of component
j is given by
(3.1.A.3)
where Mp is the atomic weight of the pth element. If the extent of reaction
changes by an amount dx, the corresponding mass change is
dm =Ldnj~ = dxLOj~
k k
(3.1.AA)
which shows that the mass conservation is implied by equation (3.1.4). However,
dm could be zero under milder conditions, since the sum over j could well be
zero without each individual addend being zero.
Suppose M = N - 1. The axiom of permanence of atoms requires equation
(3.4.1) to be satisfied for all values of k and p. If equation (3.4.1) is divided by
'TNP, with aJ = 'TJp/ 'TNP it reduces to
(3.1.A.5)
This is a system of M equations for the N - 1 unknowns aJ which has a unique 75
solution. Thus the brute chemical formulas of all components are multiples of
Homogeneous
each other, i.e., the components are either isomers or polymers of each other. Reactions
An "equilibrium state" {p*, T*, x*} is one at which the reaction rate vector
is zero, i.e.,
r(p*, T*,x*) = 0 (3.2.4)
8* = 0 (3.2.8)
Equation (3.2.8) only follows from the assumed invertibility, and hence it
is a result which is derived from the consideration of kinetics, albeit only in a
neighborhood of equilibrium. The significance of the assumption of invertibility
is discussed in some detail in the Appendix.
We note that equation (3.2.2) implies that, in all processes for which p and
T are constant, the free enthalpy can never increase. It follows that of all states
corresponding to assigned values of p and T, the equilibrium state has the lowest
free enthalpy. It also follows that cyclic reactions are impossible in the absence
of a simultaneous and independent source of irreversibility. Indeed, consider the
M-dimensional reaction subspace. Equation (3.2.2) guarantees that free energy
is a Liapunov function over this subspace for the rates of change of the space
coordinates. The cyclic reactions acting as internal clocks in biological systems
can occur only because such simultaneous alternate sources of irreversibility are
present as a result of the metabolism. This conclusion also shows that the
thermodynamics of biological reactions cannot be developed on the basis of
simple systems such as that considered in this section.
From a conceptual viewpoint, the subject matter of the thermostatics of
homogeneous reactions is exhausted by equation (3.2.8). In practice, one wishes
to solve the following problem. Given an initial composition, the reaction subspace
is identified by equation (3.1.9). Given p and T, one wishes to find the point in
this reaction subspace for which equation (3.2.8) is satisfied, say the point
corresponding to the lowest free enthalpy. In order to solve such a problem, one
needs to know the constitutive function which delivers 8 as a function of the
state. Some fundamental concepts of the theory of constitutive equations for
mixtures are discussed in the next section.
It is noteworthy that the approach discussed in this section is not restricted
to the case of chemical reactions, but applies to any system for which internal
state variables can be identified. For any such system, the second law reduces to
the requirement that the scalar product of the affinity vector with the rate of
change of the internal state variables vector should be nonpositive. An assumption
of invertibility near equilibrium, analogous to equation (3.2.7), will always pro-
duce the equilibrium condition that the affinity vector is zero. Conversely, if the
second law for any system can be reduced to the requirement that the scalar
product o( two vectors, one of which is a vector of partial derivatives of the
constitutive equation for free energy with respect to some variables while the
other is the vector of the rate of change of those same variables, should be
non positive, the first vector is identified with the affinity and the second with the 77
internal state variables' rate of change. Homogeneous
From the rate of evolution viewpoint, there is an important aspect to be Reactions
discussed concerning equation (3.2.2). As it stands, this equation implies that the
simultaneous occurrence of several chemical reactions never results in an increase
of free energy. It does not imply that each individual chemical reaction takes
place in such a way that, by itself, it causes free energy to decrease; in other
words, the individual products 9i<Xk are not required to be separately nonpositive,
but rather only their sum. This could also be worded in a different way: The
individual products -9i<Xk represent the individual rates of dissipation; the second
law does not exclude the possibility that some individual rates of dissipation may
be negative, through coupling with simultaneous chemical reactions, provided
the total rate of dissipation is nonnegative. In actual fact, the literature on
chemistry almost always makes the assumption that each individual chemical
reaction takes place in such a way as to result by itself in a nonincreasing free
energy; this poses a more restrictive constraint on possible paths in the reaction
subspace than the second law by itself would imply.
Appendix
This equation determines an intrinsic time scale for the reaction, 1/ k*. Seen
in this light, the assumption of invertibility may appear to be very strong, since
a simple counterexample comes immediately to mind: an irreversible dimerization
reaction, for which one would write r as kc 2, with k a "second-order" kinetic
constant. Quantity kc 2 is of course not invertible at equilibrium (c = 0). However,
this is an artifact of the assumption that the reaction is irreversible. In fact, let
the reaction be reversible, so that its rate would be given by kc 2 - kC2/ K, where
C2 is the concentration of the dimer and K is the concentration-based equilibrium
constant. The equilibrium concentration of monomer, c*, is of course given by
C*2 = e2/ K, and hence the rate can be written as k(e 2 - C*2). Now let the actual
concentration be very close to equilibrium, say e = c* + h, with h« c*. One
obtains
r = 2ke*h + O[(h/e)2] (3.2.A.2)
which is indeed linear in h, the displacement from equilibrium, and is invertible.
The constant k* is thus identified with 2kc*, which is clearly degenerate for a
truly irreversible reaction (e* = 0). However, real reactions are never truly
irreversible, and thus no problem arises. Of course, for an almost irreversible
reaction, one would not use k* in the description of the kinetics, but that does
not mean that there is not a finite (if very small) value of k*.
78 Next we consider the case of two reactions and suppose that, in a neighbor-
hood of equilibrium, the reaction rates are given by
Chapter Three
(3.:U.3)
and
(3.l.A.4)
Now the invertibility condition is violated, in spite of both rates being linear
in the displacements from equilibrium, and the condition in equation (3.2.6) is
satisfied with
A· dx= 0 (3.l.A.6)
(Of course, any multiple of such a vector satisfies the same equation.) For instance,
in the case of equations (3.2.A.3) and (3.2.A.4), any vector proportional to
(1, -1/ a') gives displacements from equilibrium for which the rates are zero.
The set of vectors satisfying equation (3.2.A.6) is called the kernel of A. If A is
invertible, its kernel contains only the zero vector. Any affinity vector lying in
the kernel of A would satisfy equation (3.2.6), and hence equation (3.2.8) is the
result obtained when A is invertible. Extension to the case of infinitely many
reactions is discussed in Section 3.6.
The question of free energy being a Liapounov function is briefly reviewed
in the following. Consider two variables x and Y. and let F(x, y) be a function
of them; F(x, y) = C describes a curve in the x- y plane. Let F( ) be such that
all such curves are closed, no two of them cross each other, and if C) < C2 the'
curve corresponding to C) lies within C2 • For one particular value of C, which
by normalization can be set to zero, the ciosed curve degenerates to a point xo, Yo,
say F(xo. Yo) = o.
Now we allow the x and y variables to vary in time, where x(t) and y(t)
are the parametric equations of a curve in the x-y plane which is called a path;
the curve has an intrinsic direction identified by increasing time. Now we assume
that the path is restricted by the following requirement: if the point x(t), y(t)
lies on F = C), then x(t + a), y(t + a) for any positive a lies on F = C2 < C).
This guarantees that any path will eventually end at point Xo, Yo. and that no
path can close on itself. If these conditions are satisfied, F(x, y) is said to be a
Liapounov function for the paths.
We now let x and y be the extents of two independent reactions, and let
F(x, y) be the free energy (if V and T are held constant). The affinity vector at
any point x, y is orthogonal to the F curve through that point, and points outward. 79
Equation (3.2.2) now guarantees that the rate of reaction vector, which is tangent Homogeneous
to the path and points in its intrinsic direction, has a positive component on the Reactions
inward-pointing direction, which guarantees that free energy is a Liapounov
function for the paths in the reaction subspace. The argument is easily generalized
to the case of more than two independent reactions.
The theory of mixtures is best developed by using moles, rather than grams,
as the unit of mass. This is due to the fact that the stoichiometric coefficients of
reactions turn out to be very simple small integers if mole units are chosen.
Therefore, from this point on we will use mole units unless otherwise stated; no
confusion should arise from the fact that the same symbol, say V, is used for the
molar specific volume as has been used so far for the mass specific volume.
The fundamental concepts of the theory of mixtures are simple consequences
of the fact that most of the quantities of interest are extensive, say they are
absolutely additive functions of mass. Let n be the number of moles vector, with
components n l , ... , nN which are the number of moles of each component
present in the system at some time t, and let n be the total number of moles at
time t:
(3.3.1)
y = n/n (3.3.2)
u = p, T, n (3.3.3)
(3.3.4)
(3.3.5)
Lt=n·L' (3.3.7)
L' = 6L /6n
t (3.3.8)
If the baric derivative of equation (3.3.7) is taken with respect to njo we obtain
(3.3.9)
and hence
and
6fL/6p = V' (3.3.12)
8k = aa/aXk = I (aa/anj)(anj/aXk)
j
(3A.I)
(3A.2)
where Kk is called the (activity based) equilibrium constant for the kth reaction.
The task of calculating equilibrium compositions is now reduced to the following
two steps:
The first task will be discussed later. As for the values of quantities K k , it
is evident that they depend on the particular choice of the standard state. For
chemical reactions, the standard state is chosen as that where the pressure is one
atmosphere; this of course means that Kk is independent of the actual pressure
of the reacting mixture, and in fact depend only on temperature.
Given a chemical reaction with stoichiometric coefficients which are a linear
combination of those of other reactions, its value of Kk can be calculated from
the values for the other reactions, as can easily be seen from the definitions. This
point allows one to construct a simplified way of tabulating Kk data, discussed
below.
For any given component Bj , its "formation reaction" is defined as the
reaction which transforms the molecules of the elements into the component
considered. For instance, in the case of carbon dioxide the formation reaction is
(3.4.6)
uj = 1 (3.4.7)
and
(3.4.8)
Substitution into the definition of the standard change, while making use of
equation (3.1.4), yields
Appen~ix
CELL
FIGURE 3.5.1. Sketch of the circuit of an
electrochemical cell.
The net rate at which work is being done on the system within the cell is 85
the usual mechanical power plus the electrical power, say Homogeneous
w. = -pV;- El (3oS.:!)
Reactions
(3.5.3)
Since E" can be imposed at will without influencing the state of the system,
just as T" and V;, equation (3.5.4) shows that pressure and entropy are given by
the usual partial derivatives of the free energy function, and that the free energy
itself is in fact independent of the applied electrical potential. With this, the
second law reduces to
(8 + EzF)x" 05 0 (3.5.5)
where the affinity 8 is independent of the electrical potential, since so is the free
energy. We note that, since it is always possible to open the external circuit and
thus make x" zero, equilibrium can be achieved at any value of x. We also note
that, when one opens the external circuit, E is no longer an external state variable,
since it cannot be imposed at will in an open circuit. Thus, when R' = 00 (open
circuit), E will have some value E* which is called the electromotive force of
the reaction. The reaction rate is a function of state, i.e., it is given by
r(Y"T,E*,x) =0 (3.5.7)
8* = -E*zF (3.5.8)
() = -E*zF (3oS.9)
(E - E*)1 05 0 (3oS.tO)
since zF> o.
86 Equation (3.5.10) describes the irreversibility connected with electrochemical
Chapter Three
reactions. It implies that, when the cell is being charged (I < 0), the electrical
potential is larger than when the cell is discharged. This in tum implies that the
amount of electrical work needed to charge the cell is more than the amount that
the cell yields upon discharge.
Equation (3.5.8) is, as usual, based on an assumption of smoothness. This
should be considered in some detail. Consider a fixed triplet Yt, T, x, so that E*
is fixed at the solution of equation (3.5.7). Equation (3.5.10) now imposes a
restriction on the constitutive function r( . ), the value of which can never have
the same sign as E - E*. Thus in an I vs. E - E* plot such as in Figure 3.5.2
(at fixed Yt, T, and X, I is a unique function of E), the curve is restricted to the
two odd-sign quadrants, and thus, if sufficiently smooth, it will pass through the
origin, and hence equation (3.5.8) holds.
In actual fact, the curve does pass through the origin, but its slope at the
equilibrium point is very small, as shown qualitatively in Figure 3.5.2. Only at
comparatively large absolute values of E - E* does the intensity become reason-
ably large for practical use, and in fact the curve becomes almost vertical. Two
regions can thus be identified. The first corresponds to very small intensities, and
the curve can be approximated by a straight line through the origin:
Thus it is concluded that, by having a sufficiently large value of R', one can
charge or discharge the cell very slowly, and the rate of dissipation is quadratic
in the intensity. The time interval needed to charge or discharge the cell by a
given amount is inversely proportional to the intensity, and hence the total
dissipation is proportional to the absolute value of the intensity, and can be made
as small as one wishes.
The situation described above, however, holds only for extremely low
intensities, and in actual operation a cell will work on one of the two almost
It may frequently happen that one deals with mixtures of very many com-
ponents, which may even not all be individually known. Crude oil is a good
example of such a situation. In these cases it is useful to describe the mixture
by means of one or more distribution functions, i.e., to have a continuous
description, rather than a discrete one where some finite number of components
is kept track of. Even if the individual components of a mixture are known, if
their number is large one may wish to substitute a few pseudocomponents for
ease of analysis. A continuous description furnishes a rational method for choos-
ing the pseudocomponents, in that one can look for the appropriate quadrature
points of the resulting integrals. The mathematics involved with the continuous
description of mixtures are rather involved, and only a brief outline of the theory
is given in this section. Some mathematical technicalities are dealt with in the
Appendix.
In the case of a discrete description, jndividual components are identified
by the subscript j, which takes integer values from 1 to N; in a continuous
description, components are labeled by a variable u which takes all values over
some finite; or possibly infinitely large, range. So the specific species is B(u),
just as it is Bj in the discrete description. In the continuous description, the
composition space is infinite-dimensional.
The fundamental distribution function is the mass distribution function m(u),
which is defined as follows: m(u) du is the mass of species identified by values
of the label between u and u + dUo It is important to observe that, if one allows
any distribution function to contain also a sum of a finite number of terms each
of which is proportional to a Dirac delta function I) (u - j), the discrete description
is subsumed by the continuous one.
Let M(u) be the molecular weight of species B(u). The distribution function
of the number of moles is
f u(u)B(u) du =0 (3.6.3)
f u(u)m(u) du =0 (3.6.4)
(3.6.6)
has only the trivial solution Pk = o. We note that equation (3.6.6) must hold for
all k from 1 to N.
In the continuous description we have M stoichiometric coefficient distribu-
tion functions, and the independence condition becomes that the equation
(3.6.7)
has only the trivial solution Pk = 0 over the whole range of u values.
However, since in essence one is dealing with an infinite number of species, 89
it makes sense to consider the possibility of describing an infinite set of chemical Homogeneous
reactions. Just as the component label j of the discrete description carries over Reactions
to a variable label u, the reaction label k carries over to a variable label w which
identifies the reaction. Now consider a piecewise-continuous distribution function
of stoichiometric coefficients u(w, u) which satisfies the mass conservation
requirement for all values of w:
Then
f p(w)u(w, u) dw = 0 (3.6.10)
must, over the whole range of u values, have only the trivial solution p( w) = o.
It is now possible to introduce a distribution function of extents of reaction,
x(w, t), which is defined by the analog of equation (3.1.9):
Here, equation (3.6.11) restricts the values that n(u, t) may assume, given
the values of n(u, 0); i.e., it identifies the reaction subspace. However, now also
the reaction subspace is infinite-dimensional.
We now consider a mixture where, say, a whole series of cracking reactions
may take place, and suppose that one has chosen the carbon number as the label
w. A typical cracking reaction could be written as
but now the product species could react again. In this case, a bicontinuous
distribution of reactions would need to be considered, say a distribution function
u( w, w', u) such that
So far, only the definitions have been laid down. In order to develop a
thermodynamic theory, one needs to face several issues. First, one must decide
what is the state of a continuous mixture. Since attention is restricted to
homogeneous reactions, the development below is given in terms of free enthalpy,
and p and T are regarded as independent variables. Thus in the discrete case
the state would be p, T, D. The obvious extension to the continuous case is that
the state is p, T, n(u). This however implies that the state is not identified by a
finite number of parameters, but by two parameters and a function. It follows
that the constitutive mappings are functionals (a few fundamental concepts and
definitions of functional analysis are given in the Appendix). Thus the free
enthalpy is given by
G, = f~(u)n(u) du (3.6.11)
Homogeneous
Reactions
It follows that
f
G; = (aG/ap)p' + (aG/aT)T + ~(u)n'(u) du (3.6.29)
92 The usual argument can now be used to infer again that free enthalpy is a
potential for volume and entropy, and that the second law reduces to the
Chapter Three
requirement that the integral on the right-hand side of equation (3.6.29) should
be nonpositive. If the rate of change of n(u) is calculated from equation (3.6.11)
and substituted into the integral, one obtains for the rate of dissipation
= - J (J(w)r(w, t) dw ~0 (3.6.30)
and
r( w, t) = R{x(z, t); w} (3.6.32)
(J*(w) = 0 (3.6.35)
i.e., the equilibrium affinity is zero for all values of w. Comparing this with 93
equation (3.6.28), the equilibrium condition can be written as
Homogeneous
over the whole range of w values. This is the analog of equation (3.4.2).
The theory of the kinetics of reactions in continuous mixtures is still very
primitive, and very few problems have been tackled outside of the case where
all the kinetics involved are first-order. This case would be described, in the
discrete formulation, as follows:
rd ¥. = L kkjCj (3.6.37)
j
Appendix
r
consider the following equation:
y= f(u) du (3.6.A.l)
94 The value of y depends on which particular functionf(x) is used in perform-
Chapter Three
ing the integration, but it does not depend on u-a functional is not a composite
function. The following notation is used for a functional:
y = 1F{f(u)} (3.6.A.2)
and, as in the case of equation (3.6.A.1), the argument function need only be
defined over some range of u values [a < u < b in the case of equation (3.6.A.2)]
which is not indicated in the notation adopted unless it is not obvious from the
context.
A linear functional is one which satisfies the usual condition of linearity:
(3.6.A.3)
where the difference between two functions is defined as that function which has
value equal to the difference between the values of the two functions. Of course,
the integral in equation (3.6.A.l) is a linear functional.
From this point on, notation is simplified by using f, g, etc., for the argument
functions. The Frechet differential 811' of a functional is defined in the following
way:
but the kernel k( u) still depends on f, since so does 1l1F{ }. Hence the kernel is
a functional itself, which also depends explicitly on u as a parameter:
Dividing equation (3.6.A.10) by a-I and then taking the limit as a approaches
unity produces equation (3.6.20), with G '{ } being the functional derivative of
G{ } with respect to the argument function n (u). This is the continuous generali-
zation of the III Ilnj derivative which produces the partial molar properties.
Permanence of atoms places the following restriction on the stoichiometric
coefficient distribution:
for all wand all P, where 'Tp(u) is the number of P atoms in species u. The
molecular weight of species u is
Examples
1. Consider a mixture of methane and ethane which is sent to a reactor where the
water shift reaction is to occur, for the production of hydrogen and carbon dioxide.
Oxidation, however, can also occur to the carbon monoxide form, so that one may start
by writing the following reactions:
CH. + H2 0 = CO + 3H2
CH. + 2H20 = CO 2 + 4H2
C2H6 + 2H 20 = 2CO + 5H 2
C2H6 + 4H 20 = CO2 + 7H2
By inspection of the stoichiometric coefficients matrix, one could now find out that
its rank is 3, i.e., that one of the reactions is a linear combination of the others. This is,
however, a tedious procedure. It is easier to realize immediately that the fourth reaction
does not introduce any new component, and hence it can be dropped.
The set of the first three reactions is not, however, the best one for setting up the
problem. In fact, even in a gaseous mixture in which there are no activity coefficients to
deal with, the equilibrium condition for a reaction results in a polynomial equation with
degree equal to the largest of the sums of all positive and all negative stoichiometric
coefficients; hence the three reactions result in polynomials of degree 4, 5, and 7, respec·
tively. The system of equilibrium equations is thus equivalent to a polynomial of degree
4 x 5 x 7 = 140, for which even numerical techniques would be difficult to use to find the
only significant root. It takes a little bit of juggling around to find the following equivalent
but much simpler set:
1. CH. + H 20 = CO + 3H2
2. CO + H2 0 = CO 2 + H2
3. 2CH. = C2H6 + H2
which gives polynomials of degree 4, 2, and 2, and hence a system degree of 16.
There are six components, so that the composition space is five-dimensional. The
reaction subspace is three-dimensional. Let the components be numbered consecutively
as CH., C2H6 , H20, H2, CO, CO 2. Initially, there are M moles of ethane and R moles
of steam per mole of methane. The number of moles vector is
The solution has to be found under the constraint that all components of the number
of moles vector must be nonnegative.
Problems 97
Homogeneous
3.1. Consider a box of volume V,(t) in which reaction (3.1.1) takes place. The forward rate is Reactions
proportional to oxygen concentration, i.e.,
r F = k[02]
[C0 2]/[CO]v'[02] = K
°
At time zero, there is one mole of CO, one mole of 2, and no CO2, Temperature is constant
in time.
a. Derive the equation for the reverse rate.
b. What is the stoichiometrically possible range of x values?
c. Draw the curve representing the reaction subspace in the triangular diagram representing the
composition space.
d. Derive the equation relating x' to x and V,.
e. Determine the relationship between x* and V,. Can more than one equilibrium point exist
at some value of V;?
f. Suppose the function V,(t) is assigned. How do you calculate x(t)? Now consider the case
where the initial composition is different from the one given above, but does, however, lie in the
reaction subspace you have calculated. Does x(t) at very large t become independent of the
composition at time zero?
3.2. Consider a chemical reaction
for which the kinetics are of the standard mass action type, say the forward rate is given by
The net rate could be expressed as the rate of change of the extent of reaction x,
dx/dt=f(x), f(x*) =0
dP/dt = k,Q - k 2P
with the first term describing the higher probability of predators to reproduce when more prey is
available. For the prey, one writes
F{f(u)} = f f2(u) du
and let the norm be given by equation (3.6.A.5). Calculate the first Frechet differential, verify that R
is o<llgll>, and calculate the functional derivative. If you have done the algebra correctly, the functional
derivative should be an ordinary function, not a functional. Why is that? Construct the simplest
functional you can think of such that its functional derivative is not an ordinary function.
3.6. Consider the following functional:
F{f(u)} = f2(a)
where a is a fixed number. Now consider two metrics: one with the norm as in equation (3.6.A.5)
and one where it is given by
Ilf(u)11 = f f2(u) du
Calculate the Frechet differential via equation (3.6.A.6). Is the residual R of o<llgll> with respect to
both topologies? Comment on your result.
LITERATURE
The method of determining the rank of the stoichiometric matrix presents some
subtlety when different isomers may be present in the reacting mixture; see J. C. Whitwell
and R. S. Dartt, AIChEJ. 19, 1114 (1973).
Proof that the reaction subspace and the composition space coincide only in the case
of isomerization and polymerization reactions is given by G. Astarita, Chem. Eng. Sci. 31,
1224 (1976).
Direct coupling between different chemical reactions is generally excluded as a
possibility in the chemical literature; the point is discussed by M. J. Boudart, 1. Phys.
Chem. 87, 2286 (1983).
The implications of the strong constraint, that every individual chemical reaction
proceeds with a nonnegative dissipation rate on possible reaction pathways, are discussed
by R. Shinnar and C. A. Feng, Ind. Eng. Chem., Fundam. 24, 153 (1985).
There is ample literature on the mathematics of stoichiometry and mass action kinetics;
two important references are E. H. Kerner, Bull Math. Biophys. 34, 243 (1972) and M.
Feinberg, Arch. Ratl Mech. Anal. 49, 187 (1972).
The general case of linear kinetics is formalized by J. Wei and C. D. Prater, Adv. 99
Catal13,203 (1962).
Homogeneous
Point (e) of Problem 3.1 raises the possibility that there may be more than one
Reactions
equilibrium point in the reaction subspace. This is possible in nonideal mixtures; see H.
G. Othmer, Chern. Eng. Sci. 31, 993 (1976).
The whole question of independence of chemical reactions, the influence of
stoichiometry on the equilibrium behavior of reacting systems, and the stability of chemical
equilibrium was discussed in detail long ago by E. Jouguet, J. Ecole Poly., II Ser. 21, 61,
181 (1921); a more recent formal discussion was given by R. Aris, Arch. Ratl. Mech. Anal.
19, 81 (1965).
The general theory of homogeneous reacting mixtures, expressed in terms of internal
state variables, has an ample literature. Some important references are M. E. Gurtin and
A. S. Vargas, Arch. Ratl Mech. Anal. 43,179 (1971); B. D. Coleman and M. E. Gurtin,
J. Chem Phys. 47, 597 (1967); Phys. Fluids 10, 1454 (1967); C. A. Truesdell, Rational
Thermodynamics, 2nd ed., Chapter 5, Springer-Verlag, Berlin (1984).
The best source for the concept of affinity is Th. De Donder and P. Van Rysselberghe,
Thermodynamic Theory and Affinity, Stanford University Press (1936); the concept of
affinity, however, predates this by quite some time. The word "affinity" was used as far
back as 1888 by H. Le Chatelier, Les Equilibres Chimiques, Carre et Naud, Paris (1888),
and it was attributed to earlier workers such as Berthelot, if in derogatory terms.
The question of writing the stoichiometric equation for a reaction in the form of
equation (3.1.2), with stoichiometric coefficients which can be both positive and negative,
also has an old tradition; see, e.g., K. G. Denbigh, The Thermodynamics of the Steady
State, Methuen, Landon (1951).
This leads to the question of what is meant by the so-called "principle of microscopic
reversibility." This is discussed in the Denbigh book cited above, as well as by J. Wei, J.
Chem Phys. 36, 1578 (1962) and by G. Astarita, Quad. Ing. Chim. Ital. 14, 1 (1978).
The continuous description of mixtures was first developed by Th. De Donder,
L'affinite-Seconde Partie, Gauthier-Villars, Paris (1931). The presentation in Section 3.6,
as well as most modem analyses of continuous mixtures, is based on the methodology
discussed in the fundamental work of R. Aris and G. R. Gavalas, Phi/os. Trans. R. Soc.
London, Ser. A 260, 351 (1966); however, the second-law implications are based on the
methodology presented by Truesdell for the case of a finite number of reactions in the
book cited above. The question of substituting pseudocomponents for a mixture, by finding
the optimal quadrature points for the integrals appearing in a continuous description,
is discussed by S. K. Shibata, S. I. Sandler, and R. A. Behrens, Chern. Eng. Sci. 42, 1977
(1987).
Kinetic analyses for continuous mixtures (mostly linear kinetics) have been reviewed
by V. W. Weekman, Chern. Eng. Prog., Symp. Ser. No. 11, 75, 3 (1979) and by K. B.
Bischoff and P. Coxson, Proc. 2nd ICREC Meeting, Pune (1987). Some preliminary
analysis of the nonlinear case is discussed by G. Astarita and R. Ocone, AIChEJ. 39,1299
(1988) and by G. Astarita, AIChEJ. (to be published).
A good source for studying functional analysis is F. Riesz and B. Nagy, Functional
Analysis, Ungar, New York (1955).
Liapounov functions are discussed in all textbooks on stability analysis; a good source
is M. M. Denn. Stability of Reactions and Transport Processes, Prentice-Hall, Englewood
Cliffs, NJ (1975).
Problem 3.3 is a variation of the classical predator-prey model of A. J. Lotka, J. Am
Chem Soc. 42, 1595 (1920); Proc. Natl. Acad. Sci. U.S.A. 6, 410 (1920). In the Latka
formulation the kinetic equations are
Chapter Four
PHASES
NOTATION
Subscripts
Superscripts
T Transpose
1,2 For phase 1,2
* At equilibrium
Substantial time derivative
MIX Of mixing
Partial molar
4.1. ONE-COMPONENT,
TWO-PHASE SYSTEMS
A phase is defined as a part of a body within which the local state is a smooth
function of position (the gradient of any state variable is finite at all points). A
multiphase system is therefore a body which contains surfaces of discontinuity
for the state; such surfaces are called interfaces. The principle of action and
reaction forbids pressure to be discontinuous at interfaces, and so pressure is
continuous even in multiphase systems, except for the effect of surface tension
on curved interfaces. There is no fundamental law of physics which forbids
temperature discontinuities, but in heat transfer theory the usual assumption of
a continuous temperature distribution has been generally successful, and therefore
that assumption is retained here (see the literature section in this regard).
In this chapter, attention is focused essentially on the equilibrium behavior
of multi phase systems, and therefore an additional simplification is possible,
namely, that the state is constant in space within a phase. This in tum implies
that temperature and pressure are constant throughout a multiphase system. This
simplification is certainly valid at equilibrium (except, as far as pressure is
concerned, for the hydrostatic pressure distribution), and therefore the equili-
brium equations derived below are valid. However, the nonequilibrium results
should be regarded as only indicative of trends.
If attention is restricted to a one-component elastic system, the only state
variable is the local specific volume, and all functions of state can be regarded
as uniquely determined by the value of Y; in particular
A = a(Y) (4.1.1)
Since pressure is the same in the two phases, the same is true of the derivative
da/ dY. It follows that two phases may exist only if the a( Y) function has at
least two distinct points with equal derivative. This in tum implies that the second
derivative d 2a/ dy2 must change sign at least once. In fact, two phases will exist
under conditions where d 2 a/ dy2 changes from positive at low Y to negative and
then to positive again, as discussed below. 103
104 Let us consider the a (Y) curve in Figure 4.1.1. The derivative is always
negative, so that pressure is always positive (in actual fact, a negative pressure
Chapter Four
is not a physical impossibility if the system considered has a finite tensile strength).
The following equation holds along the entire curve:
(4.1.2)
It follows that, in the "spinodal" region, i.e., in the region where d 2al dy2 is
negative, pressure increases with increasing volume. It is easy to convince oneself
that this is a mechanically unstable condition.
Suppose the system considered exists in a two-phase condition, with the two
phases identified by points 1 and 2 in Figure 4.1.1; dal dY is indeed the same at
these two points. Let a fraction z of the total mass be at condition 1, and a
fraction 1 - z at condition 2. The total mass of the system, m" and the total
volume, Yo, are fixed. The following equation is obvious:
V;lm t = zyl + (1- z) y2 (4.1.3)
Equation (4.1.3), and the condition that dal dY be the same at points 1 and
2, poses two constraints on the values of z, Y I , and Y2 • It follows that both YI
and Y2 are determined once z is assigned. Thus, by differentiating equation (4.1.3)
with respect to z one obtains
(4.1.4)
We now consider the total free energy of the system, which is given by
(4.1.5)
(4.1.6)
A
SPINODAL
REGION
For points 1 and 2, it is easy to convince oneself that the right-hand side of
equation (4.1.6) is negative. It follows from equation (4.1.7) that z will tend to
increase, i.e., that the two points will tend to move to the right. Equilibrium is
of course reached when the two points have moved to points 3 and 4, the only
couple of points for which the right-hand side of equation (4.1.6) is zero.
Whenever the average specific volume of the system, V,I mt , is in the interval
y3 _ y\ the system at equilibrium will exist in a two-phase condition, with y3
and y4 being the specific volumes of the two phases. The equilibrium value of
z is determined by the lever rule, say it is calculated from equation (4.1.3). We
note that both y3 and y 4 lie outside the spinodal region, since d 2al dy2 is positive
at both of them. An equilibrium two-phase system can only exist if the a( Y)
curve has a spinodal region, but the specific volumes of the two phases at
equilibrium are not spinodal points.
If Figure 4.1.1 is regarded as relative to a liquid-vapor system, the branches
of the curve are related to the branches of the curve in Figure 2.6.1; indeed, the
latter is nothing else than minus the derivative of the former. For Y values up
to y3, the curve is an equilibrium curve, with z = 1 (pure liquid). For Y values
between y3 and the first spinodal point, the curve is the nonequilibrium curve
of a superheated liquid; for values between y4 and the second spinodal point,
it is the nonequilibrium curve of a supercooled vapor. Finally, at values from y4
upward, the curve is the equilibrium curve for a gas (z = 0).
The right-hand side of equation (4.1.6) is the difference between the free
enthalpies of the two phases. It follows that, at equilibrium, the free enthalpies
of the two phases are equal. Pressure and free enthalpy are the only two constitu-
tive properties which, at equilibrium, are equal in the two phases .
. Now consider a one-component, one-phase system at some fixed pressure.
Since the baric derivative of free enthalpy with respect to temperature is minus
the entropy, it is intrinsically negative, i.e., the free enthalpy decreases with
increasing temperature (see Figure 4.1.2). At any given temperature, the equili-
brium phase is the one endowed with the lower free enthalpy. It follows that, as
temperature is increased, a phase transition will occur when the two curves
PH SE I
DG=Dp=O (4.1.8)
DU=DH-pDV (4.1.10)
DA=pDV (4.1.11)
(in the case of a liquid-vapor transition, p* is called the vapor pressure of the
liquid). Let us consider a differential change in temperature dT. If the system is
to remain in an equilibrium two-phase condition, the corresponding dp is given
by (dp* / dT) dT, and hence the free enthalpy change in both phases can be
written as
dO = [50/ ilT + (50/5p) dp*/ dT] dT
= [-8 + Vdp*/dT] dT (4.1.13)
But the dO for the two phases must be the same, since they are kept in
equilibrium with each other. It follows that
which is called the Clausius-Clapeyron equation. For those transitions (like ice
melting) for which DV is negative, so is dp* / dT: at high pressures, ice melts at
temperatures lower than O°C. For vapor-liquid transitions, the vapor pressure
always increases with increasing temperature (see Section 4.5 for a more detailed
discussion of this point).
At very low temperatures (lower than the triple-point temperature), the a( V)
curve may present one or more spinodal regions corresponding to solid-solid
transitions. These are followed by a spinodal region corresponding to a solid-gas
transition, which is called a sublimation. At temperatures exceeding the triple-
point temperature, a solid-liquid transition occurs between the last solid-solid
one and the liquid-vapor one. (It will be seen in Section 4.4 that liquid-liquid
transitions are sometimes observed as well.) As the temperature is further
increased, the spinodal region of the liquid-vapor transition becomes progress-
ively smaller (DV decreases with increasing temperature) until a temperature is
(4.2.1)
The usual argument shows again that the first two terms in equation (4.2.3)
are identically zero. Furthermore, we note that, if no chemical reactions occur,
the only way for n' to change in time is by transferring components to or from
the other phase. Hence
(4.2.4)
(4.2.5)
Equation (4.2.5) imposes a restriction on the mass transfer vector n'·. This
equation does not require that mass transfer of each component individually
should be toward the phase for which the chemical potential is lower, but only
that the scalar product of the affinity (or driving force) vector ... ' _ ... 2 with the
mass transfer vector should be nonpositive.
The vector n' can be regarded as the internal state variable, and therefore
the driving force vector is the affinity. Again under sufficient assumptions of
smoothness near equilibrium [perfectly analogous to those leading to equation
(3.2.8)], one concludes that the equilibrium affinity is zero, i.e.,
(4.2.6)
(4.2.7)
since
(4.2.8)
Now suppose that, as long as the system is in a one-phase state, the free
enthalpy density as a function of YI is as plotted in Figure 4.2.1. Since free
enthalpy is only defined to within an arbitrary additive quantity which need not
be the same for two different one-component systems, the curve in Figure 4.2.1
is to be understood as significant to within addition of an arbitrary straight line
(or, in other words, the values of G atYI = oand atYl = 1 are arbitrary). Therefore,
any conclusion drawn from the figure must be invariant with respect to such an
additive straight line. For instance, statements about the curvature are invariant.
The statement that the slope is equal at two points is invariant, but the actual
value of the slope is not.
Now let us assume that, for any reason whatsoever, the system unmixes to
a two-phase state. The free enthalpy of each phase will be a point on the curve,
but the average free enthalpy density of the two-phase system will not, and it
will be given by the usual lever rule construction from the points representing
the two phases and the assigned average value of YI. This leads, for example, to
the average free enthalpy density at point A for a two-phase condition character-
ized by points Band C and the average mole fraction D. We note that, in the
interval of YI values over which the curvature of the G curve is negative, this
construction leads to a free enthalpy of the unmixed system lower than that of
the one-phase state, even if the two phases have compositions which are only
differentially diverse from each other. This means that even an infinitesimally
small unmixing (which can always occur simply by Brownian motion) will result
in a decrease of free enthalpy. It follows that the one-phase state is locally
unstable to unmixing (the term '''diffusional instability" will- be used in the
following), in the sense that it is unstable to infinitesimal disturbances.
The two points of inflection of the G curve are again !lalled spinodal points,
and the region between them is called the spinodal region. Consider now point
E, which is outside the spinodal region. It represents a locally stable one-phase
SPINODAL
REGION
(4.2.11)
The left-hand side of equation (4.2.11) is simply the slope of the G curve,
while the right-hand side must have the same value in the two phases at equili-
brium. Of course, couples of points with equal slope other than F and H do exist,
but only the pair F/H is such that not only is the difference between the two
chemical potentials equal, but also their individual values.
Points on the G curve outside the spinodal region but inside the F I H interval
are metastable. If the system exists in a metastable one-phase state, in order to
unmix toward the equilibrium state the second phase needs to nucleate, i.e., a
finite disturbance is needed. Nucleation is often the governing step in unmixing
phenomena, and in fact it normally would not take place at all, or with great
difficulty, in the absence of nucleation sites (microscopic solid grains, irregularities
ofthe surface of a bounding solid, and so on). In contrast with this, points within
the spinodal region can only exist in nature long enough to be observable if
growth of nuclei is sufficiently slow (as is the case in solids), since nucleation
would occur spontaneously under the influence of Brownian motion.
It is comparatively easy to generalize the analysis given above to the case
of a mixture with an arbitrary number of components. Let Go be the vector whose
components are the free enthalpy densities of the pure components. Should free
enthalpy be additive, the free enthalpy density of a mixture with composition
identified by the mole fraction vector y would be given by
G = y·G o (4.2.12)
(4.2.13)
(4.2.14)
The free enthalpy for the system consisting of such separated mixtures is
simply the sum of their free enthalpies, and is thus obtained by the multi-
dimensional generalization of the lever rule:
(4.2.15)
If all sucli mixtures are mixed together, the resulting mole fraction vector is
(4.2.16)
(4.2.17)
Appendix
where the y(u) functions are of course restricted by the requirement that
f y (U)dU=1 (4.2.A.3)
(4.2.A.S)
for any set of Cl!K satisfying equation (4.2.14); i.e., the functional G MIX{ } has
to be convex over the space of argument functions satisfying equation (4.2.A.3).
(4.3.2)
and the multiplication involved is that of the M x N matrix 0' T and the N x 1
matrix of the components of .....
The second law reduces again to equation (4.2.3), and the usual argument
shows that the first two terms are identically zero, so that
(4.3.3)
(4.3.4)
and
(4.3.5)
(4.3.6)
(4.3.7)
(4.3.9)
(4.3.10)
1. They must both lie on the two-phase envelope curve, and be on the same
tie line (i.e., they are in physical equilibrium with each other).
2. The tie line connecting them must cross the vertical line, since the average
composition of the system is restricted to that line.
3. Of all tie lines satisfying (1) and (2), the equilibrium one corresponds to
the lowest total free enthalpy, as calculated from the lever rule at the
intersection with the vertical line.
4-n-pentyl-cyanobiphenyl: solid-N-isotropic
Cholesteryl benzoate: solid-C-isotropic
Ethyl-p-azoxycinnamate: solid-SA-isotropic
Cholesteryl myristate: solid-SA-C-isotropic
Terephthal-bis-4-n-butylaniline: solid-SB-SC-SA-N-isotropic
For all the examples given above, the phase transitions are "reversible" in
the same sense as ordinary phase transitions are: the indicated sequence is traveled
from left to right on heating, and from right to left on cooling; however, supercool-
ing is commonly observed, particularly in the liquid crystal-solid transition. Such
reversible behavior is referred to in the specialized literature as enantiotropic.
For other one-component systems, a behavior is observed which is called
monotropic. The typical example is cholesteryl nonanoate (CN). Solid CN melts
into a cholesteric liquid crystal at 78.6 DC; transition to the isotropic form occurs
at 91.2 DC. Upon cooling at a sufficiently slow rate, the isotropic liquid transforms
to the cholesteric crystal at 91.2 cC. However, when the C form is cooled, no
matter how slowly, it does not solidify at 78.6 DC, and undercooling occurs down
to a temperature of 75.5 DC, when a transition to a smectic A liquid crystal is
observed. The solid can only be obtained by further cooling the smectic phase.
The behavior of monotropic systems can be understood with reference to
Figure 4.4.1. The uppermost curve represents the free energy function at some
high temperature where two ordinary phase transitions would be observed. As
the temperature is lowered, the intermediate valley moves up with respect to the
Some systems, particularly in the solid state, exhibit phenomena which can
be regarded in some sense as phase transitions, but are however quite different
from the ordinary ones. Such phenomena have been called higher-order phase
transitions, lambda transitions, and so on. Theoretical analyses of such transitions
have been presented in the literature, and these can be broadly classified in three
fundamental categories: theories of n-order phase transitions, nonequilibrium
theories, and supercritical theories. A brief discussion of the whole subject is
given in this section.
Let us consider an ordinary phase transition of a one-component system. At
equilibrium, pressure, temperature, and chemical potential are continuous
120 through the phase transition, and one can therefore regard the equilibrium free
enthalpy G* as a function of T and p. At constant pressure, G* is a continuous
Chapter Four
function of temperature, but its first derivative (which is minus the entropy)
suffers a discontinuity at the phase transition. Analogously, G* is, at constant
temperature, a continuous function of p, but its first derivative (the volume)
suffers a discontinuity at the phase transition. For the special phase transitions
considered in this section, volume does not suffer a discontinuity, but the second
derivative of the free enthalpy with respect to volume, namely
(4.5.1)
(4.5.2)
Da = D{3(dp*/dT) (4.5.3)
where
Va = t3V/t3T and V{3 = -t3V/t3p (4.5.4)
and
Dcp = Da(dp*ldT) + DT'(dx*ldT) (4.5.8)
where
T = liV/lix and T' = liSllix (4.5.9)
This seems to dispose of the paradox, but there is a subtlety involved. The
affinity 6 = liG / lix should, at equilibrium, be zero. Now T = li6/ lip and T' =
-li61 liT, and hence if the system were at equilibrium one would again obtain
the Ehrenfest relations. Indeed, it is quite likely that glassy polymers are not
equilibrium phases.
If one allows for more than one internal state variable, one could get by
with an equilibrium theory by postulating that the kinetic equation is not invertible
at the equilibrium point (see the discussion in Section 3.2). However, this seems
to be a rather artificial way of dealing with the matter. In spite of these conceptual
difficulties, n-order theories have been generalized to orders higher than two, by
considering the possibility that derivatives of G of higher order than the second
are the first to suffer a discontinuity.
There are two other types of difficulties with the n-order transition kind of
theory. The first is as follows. In ordinary phase transitions one can, as discussed
in Section 4.1, simply assume that the state for a homogeneous system is the
ordered pair V, T, and then proceed to show that, if a spinodal region exists in
the isothermal A- V plot, the homogeneous state may be unstable to unmixing,
and therefore equilibrium states corresponding to two phases may exist. In
contrast with this, if one accepts the second-order phase transition theory as
sketched above, the assumption that for a homogeneous system the state is the
ordered pair V, T simply leads to consideration of the case where the A- V curve
may present a discontinuity of the second derivative. This would not lead to the
consideration of instabilities possibly resulting in phase separation, but simply
to the fact that, at any given pressure, the state is either that of phase I or of
phase II according to whether temperature is larger or smaller, even by an
infinitesimal amount, than the equilibrium transition temperature, and vice versa.
There would be no equivalent of the supercooled vapor or superheated liquid
concept. This point deserves some detailed discussion.
122 Consider a system which is just at the transition condition as identified by
values v'o and To of total volume and temperature; the latter is uniform in space.
Chapter Four
Let the superscripts I and II identify the behavior at temperatures immediately
above and below To, and suppose that the system exists in a "two-phase"
condition, i.e., part ofit exhibits type-I behavior and another part type-II behavior.
Since DV = 0, the specific volume is constant in space. Hence, if indeed the state
is simply V, T, the state is constant in space-and therefore one cannot identify
the existence of two phases in the sense of the definition given in Section 4.1,
since there is no surface of discontinuity of the local state. The only properties
which are different in the two "phases" are those which are not defined at that
state-the A- V curve has a discontinuous second derivative at the transition,
and the two regions simply exhibit the values corresponding to the second
derivative to the right and to the left. It is easy to convince oneself that the
relative amount of the two "phases" is in fact indeterminate. If even a differentially
small amount of heat is added to the system, the region of type-II behavior will
simply disappear since, if indeed the latent heat is zero, addition of heat will
result in an increase of temperature. The same is true if temperature is held
constant and the volume is changed by even only a differential amount.
The above point is clarified by consideration of the rate of "phase transition."
Consider first the case of an ordinary phase transition such as the freezing of
water. Suppose a semi-infinite body of water located at y > 0 is initially at the
freezing point (O°C), while at time zero the plane y = 0 is brought to some
temperature lower than 0 °C and thereafter maintained at that temperature. A
layer of ice will start to grow, through wtpch unsteady heat conduction carries
heat from the freezing surface located at y = l(t) to the cold surface at y = o.
This is the classical Stefan problem, which is formulated by assuming that the
temperature at the freezing surface is the equilibrium freezing temperature, i.e.,
o°C. The freezing surface thus advances at a rate governed by the rate at which
the latent heat DH is removed by heat conduction, say a situation in which the
following boundary conditions are imposed on the differential equation for
unsteady heat conduction:
Should a transition of the type discussed above take place the problem could
not be formulated in the same way, since equation (4.5.10) would yield an infinite
4
Cp I
I
I
I
I
7
I
II
FIGURE 4.5.1. Specific heat vs. temperature for
To T a system exhibiting an ordinary phase transition.
rate of advance of the freezing surface-the whole semi-infinite body would be 123
predicted to instantaneously undergo the transition as soon as the surface y = 0
Phases
is cooled below the transition temperature. The difficulty can be circumvented
by allowing the temperature at the transition surface to differ from its equilibrium
value, while assuming that the rate at which the transition takes place is governed
by the local undercooling. This corresponds essentially to regarding the system
as one endowed with an internal state variable, the rate of change of which is
the rate of phase transition.
The question of whether the latent heat is in fact zero in the special transitions
discussed here is a delicate one. In ordinary phase transitions, the equilibrium
enthalpy H* suffers a discontinuity. For instance, its value at a given pressure
could be expressed as
where fl( ) is the Heaviside step function, 11 is zero at T > To, and 12 is zero
at T < To. Correspondingly, the specific heat at constant pressure is
(4.5.12)
where 8( ) is the Dirac delta function; the equilibrium specific heat exhibits a
delta spike at the phase transition. The behavior is of the type shown in Figure
4.5.1. We note that, on both sides of the transition, the specific heat is a quite
smooth function of temperature.
In some special transitions, the specific heat curve has the shape shown in
Figure 4.5.2 (which justifies the name of lambda transitions sometimes given to
the transitions). The shape of the curve as given in Figure 4.5.2 is, qualitatively,
what is observed for the transition that liquid helium undergoes at 2.2 K, and
for one of the solid-state special transitions of quartz. Whether the specific heat
actually becomes infinitely large at To is open to question, and the point is of
course not possible to settle by experiment; however, it certainly becomes very
large indeed, and the behavior is thus similar to that observed in supercritical
conditions. This is the basis of the supercritical theories of special transitions.
Such theories are essentially theories where the two "phases" are not regarded
~s truly different phases, but simply as conditions on the two sides of a region
(4.5.13)
since, of course,
(4.5.15)
(4.5.17)
These quantities will of course differ without any need for the v( ) function to
be anything but perfectly smooth. The same argument applies also to a and cpo
The analysis below is based on the hypothesis that indeed all l( ) functions of
interest are smooth, and that any observed discontinuity at the transition is simply
related to the fact that one measures derivatives of the 1*( ) functions above it
and derivatives of the l( ) functions below.
We now let [L] represent the difference between the measured values of L 125
in the rubber phase and the glass phase. The notation DL is avoided, because
Phases
[L] is a difference between measurable quantities while DL represents an actual
difference in values of a function l( ) at the transition, and such differences
have been assumed not to exist. For the case of two internal state variables X
and Y (the reason for choosing two internal state variables will become clear in
the following) equations (4.5.16) and (4.5.17) yield
(4.5.18)
and analogous equations can be written for [cp ] and [a]. For the latter, in fact,
two equations can be written, since VT = -sp; so we obtain
However,
gxxx; = -vx (4.5.22)
and
gxxx:} = Sx (4.5.23)
(4.5.25)
where equation (4.5.26) is obtained from both equations giving [a]. Since all
quantities are to be calculated at the transition itself, the second derivatives of
g are positive, and hence equations (4.5.24) and (4.5.25) imply that [f3] and [cp ]
are positive, as indeed is observed experimentally. No constraint is predicted
concerning the value of [a], though the latter is in general also measured as
positive. However, one cannot exclude that a special transition with [a] < 0 may
exist, just as ordinary phase transitions with DV < 0 exist.
By substitution and algebraic rearrangement one obtains
(4.5.27)
Examples
1. Consider water at its triple point, in a condition where ice, water, and steam are
simultaneously present. Two examples concerning such a system will be discussed. First,
consider the case of a very damp winter morning; there is some partially melted ice on
the ground, and let us assume that the humidity is 100%. We are therefore in the presence
of all three phases, and yet, quite obviously, pressure is 1 atmosphere, i.e., it is not the
triple-point pressure for water. Furthermore, the ambient temperature may well not be
the triple-point temperature. How do we explain the situation?
First consider the case where the temperature is indeed the triple-point temperature.
This is trivial: it is an equilibrium situation, with the partial pressure of water vapor in
the air being equal to the triple-point pressure. If the temperature is, say, higher than the
triple·point temperature, the system is not in equilibrium, and heat transfer from the
ambient to the ice-water interface will result in a finite rate of melting; it is still reasonable
to assume that the temperature at that interface is the triple-point temperature (see Chapter
7 for more details on this point).
2. Now consider the case where a closed constant-pressure box contains only ice,
water, and steam at the triple-point temperature and pressure. Suppose some heat is added
very slowly, not enough to make any of the three phases disappear. Is ice going to melt,
water to evaporate, or some combination thereof?
Should the constraint be that the box has a constant volume, the problem would be
trivial. Sayan amount Q of heat is added. Let DVM be the volume change of melting
(which is negative for water) and DVv the volume change of vaporization; and let DHM
and DHv be the corresponding enthalpy changes (or latent heats). The two equations
(4.E.l)
and
(4.E.Z)
determine uniquely the values of the number of moles melted, nM , and of the number of
moles vaporized, n v. However, the constraint is that of constant pressure, and it is easy 127
to convince oneself that one cannot write down two independent equations which determine
the values of n M and n v. It is possible to fool oneself that one has written two such Phases
equations, or some set which solves the problem, but on close inspection it will tum out
that the equations which have been written are not independent of each other.
The problem is related to the fact that pressure is not an external state variable but
a function of state. One should ask oneself how would one actually conduct a constant-
pressure experiment. An approach would be to imagine that one has a frictionless piston
with a fixed weight on it. However, frictionless pistons do not exist in reality. Another
way would be to consider a piston with friction, which is controlled by a pressure transducer
signal. The control would never move the piston unless pressure changes from the set
value; as long as heat is added slowly, so that the system is always at equilibrium, pressure
would always be equal to the triple-point pressure, and therefore the control would never
move the piston. Hence the real constraint is a constant-volume one, and the solution is
trivial.
This example is meant to illustrate the actual meaning, of pragmatical engineering
significance, of the fact that volume is indeed an external state variable, while pressure
is not. The following example stresses the same point.
3. In the late 1970s, the Seveso accident took place. A chemical reactor exploded
during the night, when the plant was shut down, and a very toxic chemical was spread
over a vast area, resulting in very major damage. The reactor was supposed to be a
constant-pressure one, and hence one which could not possibly explode. The constant-
pressure device was extremely simple: a two-inch-diameter tube which vented the reactor
to the atmosphere.
What happened was that, in the liquid left in the vessel, some very fast chemical
reactions occurred and produced a large amount of gaseous components. These could, of
course, escape through the two-inch tube; however, the highest possible velocity through
a tube is the velocity of sound, and the rate of production of gaseous components exceeded
the corresponding highest possible ftowrate through the tube. This is known because an
acute whistling noise was heard immediately before the explosion. Pressure within the
vessel therefore increased well above atmospheric pressure, and the explosion could occur.
Problems
4.1. In the usual pressure-temperature plot, phase transitions are identified by lines, since
pressure is the same in the two phases. The lines represent the equilibrium pressure at which the
transition occurs. One can construct also a temperature-volume equilibrium plot. In such a plot,
curves would represent loci of equilibrium points of the isothermal a (V) curves. These curves delimit
regions in the V - T space where, at equilibrium, the system is in either a one-phase or a two-phase
state, such as a gas region, a gas-liquid region, and so on.
Consider two different one-component systems. Both have only one solid equilibrium phase; for
one of them the DV of the solid-liquid transition is positive, for the other it is negative. Draw
qualitative pressure-temperature and temperature-volume equilibrium plots for both systems.
4.2. Consider a two-phase system in which both heat and mass transfer are taking place. Only
one component is transferred between phases. In developing this problem, use the same approach
as taken in this chapter: the local state is uniform in both phases, but it suffers a discontinuity at the
interface, and in particular both the chemical potential of the transferring component and the
temperature are discontinuous across the interface. (This corresponds to neglecting the temperature
and concentration boundary layers near the interface.) The quantities of interest are: the heat transfer
rate q, the mass transfer rate N, the two chemical potentials of the transferring component in the
two phases, and the temperatures ofthe two phases. The system as a whole is maintained at constant
volume and is adiabatic.
128 a. What form does the second law take?
h. When the two temperatures are equal, is the heat transfer rate necessarily zero? Conversely,
Chapter Four if the two chemical potentials are equal, is the mass transfer rate necessarily zero?
4.3. It has heen observed for some gas-liquid systems that the dynamic surface tension s is
different from the static one s*. The static surface tension is that observed when the interface area
l: is constant in time. The following equation has been proposed for the dynamic surface tension:
s = s* + /L,l:'
LITERATURE
The idea that a one-component system has in principle properties which are continuous
through the phase change, embodied in Figure 4.1.1, is originally due to Van der Waals,
Die Continuitat des Gas!ormingen und Flussigen Zustandes, J. A. Barth, Leipzig (1881).
The question of pressure and temperature being continuous across an interface
between two phases presents some subtlety. For instance, shock waves in gases are
phenomena where both temperature and pressure are discontinuous; however, the discon-
tinuity travels through the gas and is sustained by a nonequilibrium phenomenon. The
point is discussed in detail in any book on gas dynamics. Discontinuities of temperature,
chemical potential, and velocity can also occur in nonequilibrium phenomena; the whole
question is discussed in a recent review paper by G. Astarita and R. Ocone, Adv. Chern.
Eng. (to be published).
Phase equilibria are discussed in all thermodynamics textbooks. For the case of
mixtures, a very complete discussion is given by M. B. King, Phase Equilibria in Mixtures,
Pergamon Press, Oxford (1969).
Phase equilibria in continuous mixtures have been discussed in a number of papers;
the recent one by S. K. Shibata, S. I. Sandler, and R. A. Behrens, Chern. Eng. Sci. 42,
1977 (1987) is a good guide to the relevant literature.
The possibility of heterogeneous isomerization equilibria has been considered by H.
S. Caram and L. E. Scriven, Chern. Eng. Sci. 31, 163 (1976); see also G. Astarita, Chern.
Eng. Sci. 31, 1224 (1976), and the literature cited in these papers.
A comparatively recent review on liquid crystals is to be found in G. W. Gray and
P. A. Winsor (Eds.), Liquid Crystals and Plastic Crystals, Ellis Horwood, Chichester (1974).
Special transitions are discussed by H. B. Callen, Thermodynamics, Wiley, New York 129
(1960); L. Tisza, Phase Transformations in Solids, Chapter 1, Wiley, New York (1951);
and K. Denbigh, The Principles of Chemical Equilibrium, Cambridge University Press, Phases
Cambridge (1964). The specific case of the rubber-glass transition in polymers is discussed
in detail by R. N. Haward, The Physics of Glassy Polymers, Applied Science Publ., London
(1973). The literature which deals specifically with the problem of predicting inequalities
such as 1T;;" 1 is extremely confusing, and much of it is best left unread.
Chapter Five
THERMODYNAMICS OF
RELAXATION
NOTATION
Subscripts
Superscripts
t, T History at time t, T
* At equilibrium
Substantial time derivative
Operators 133
Thermodynamics
1·1 Modulus (or absolute value)
of Relaxation
S· Frechet differential
11·11 Norm
.
[ ] Jump
S/St Invariant time derivative
D( ) Distance
5.1. INTRODUCfION TO RELAXATIONAL
SYSTEMS
which shows that equilibrium will be reached over a time scale of order 6.
Now consi4erthe case where V; is changing in time in some arbitrary fashion.
Equation (5.1.2) can be rearranged as follows:
Equation (5.1.4) has the obvious integrating factor exp(tI6), so the solution is
This equation should be examined in great detail. First of all we note that,
when t is significantly larger than 6, the value of x becomes independent of its
initial value Xo. Furthermore, since the value of F is bound to be between 0 and
1, at large values of t the value of the integral is dominated by the values of the
integrand near the lower limit of integration. What is implied is that, at any given
time t (provided it is large as compared to 6), the value of x is determined
entirely by the values of V; in the last several units of time, and is independent
of the values that V; may have had in the very distant past. Indeed, s is a time
variable which measures, at any given instant of observation t, "how long ago"
a given value of V; was assigned. In this interpretation, exp( -sl 6) is seen to
represent how well events occurring s time units ago are remembered. The system
has a "fading memory": volumes imposed shortly ago do influence the present
state, but those imposed in the distant past do not.
Since equation (5.1.4) admits a simple integrating factor, its solution is in
terms of an explicit integral; this is, however, related to the very simple form of
the kinetic constitutive equation (5.1.2). More complex kinetics would result in
a differential equation, which may well not admit an integrating factor. Now the
integral on the right-hand side of equation (5.1.5) is a very simple functional of
F[ ] (in fact, it is its Laplace transform). For more complex kinetics, the solution
may not be expressible as an integral, but it is perhaps obvious that it will in any
case be representable as a functional of the F[ ] function. This clarifies why
functional analysis is crucial to the thermodynamics of relaxation.
We now consider the following possibility. For the system under consider-
ation, we do not know that there is an internal state variable, and even less do
we have equations for its rate of evolution in time and for the equilibrium function.
We are undertaking isothermal experiments, and we are simply trying to find out
what the pressure-volume relationship may be. Since x is a· state variable, the
instantaneous value of pressure depends also on X, and therefore the consider-
ations made in the preceding paragraph apply to pressure as well.
At the beginning of our experiment, the results will not make any sense at 137
all since they will depend on what volumes were imposed on the system prior
Thermodynamics
to the beginning of the experiment; these volumes are not known (should they of Relaxation
be known, the actual experiment has really been started earlier). In the following,
we discuss the kind of results we would obtain in different experiments.
The simplest experiment would be one where we simply keep the volume
constant. In such an experiment, x would vary in time according to equation
(5.1.3), and therefore we will record a pressure that changes in time and
approaches asymptotically some final value p*; the time scale of this phenomenon
will be 8. It is obvious that the system cannot be described by an elastic theory,
since at a given value of volume different pressures are exhibited. However, also
a viscous theory is inadequate: at assigned values of both volume and its rate of
change (the latter being assigned a value of zero), different pressures are exhibited.
Neither is there any hope by considering some extension of a viscous theory
where higher-order time derivatives of volume are included into the state, since
all of those are kept at a value of zero while pressure is changing. Hence the
need for a theory of higher complexity is made evident (if the existence of an
internal state variable is either unknown or difficult to model).
Another possible experiment is one where, after the volume has been assigned
in some arbitrary fashion for some time, it is suddenly changed by a finite amount
over a time interval negligibly small as compared to 8. Such a volume change
could be regarded as being instantaneous, and consideration of equation (5.1.4)
shows that, in response to such a change, x would not vary, but only dx/ dt would
suffer a discontinuity. However, pressure does depend on the instantaneous value
of V as well as on x, and thus we would observe that, in response to an
instantaneous change of volume, pressure also undergoes an instantaneous
change, followed by a relaxation phenomenon. In this section we try to avoid
mathematical technicalities; however, in some sense the result of the experiment
just described would convince us that the instantaneous value of V has special
relevance, and thus we would conclude that the isothermal equation of state for
pressure is of the following form:
where ~ is a functional of the function Y,(t - s), whose value also depends
parametrically on the instantaneous value Y,(t).
The fact that the instantaneous value of volume at time t appears explicitly
as an argument of the functional needs to be discussed in some detail. Suppose
that, at some time t - s previous to the instant at which pressure is being measured,
the volume had been given a spike such as is shown in Figure 5.1.1. Such a spike
would have no effect on the pressure at time t, since it would contribute nothing
to the integral in equation (5.1.5). In contrast, a volume spike at time t would
result in a pressure spike, and this is the reason why the instantaneous value of
the volume appears explicitly as an argument in equation (5.1.6) [the exact
mathematical definition is that the functional in equation (5.1.6) is smooth except
for an atom at time t; see also the Appendix for more details on this point].
By additional experiments we would convince ourselves that, no matter
which Y,(t) function we impose on the system, the pressure exhibited at any
138 v
Chapter Five
I
I
I
I
I
S I
----1I
I
given instant only depends on the volumes we have assigned over the past several
time units. This observation could be incorporated mathematically in equation
(5.1.6) by techniques of functional analysis which will be discussed in the next
section.
So far, only isothermal experiments have been considered. Now suppose we
start conducting experiments where also temperature is allowed to change. We
would begin by again undertaking the simple equilibrium experiment at some
other fixed temperature. For the concrete system we are considering, the value
of (J would now be different, and presumably smaller if the temperature has
been increased. So we would conclude that the "relaxation time"-the time
scale needed to reach equilibrium isothermally-is a decreasing function of
temperature.
In some other experiment, we will change temperature with time in some
arbitrary fashion while keeping the volume constant. Now the values of both x*
and (J on the right-hand side of equation 5.1.2 are changing in time, and therefore
the value of x at anyone time would depend on which temperatures we have
assigned in the last several units of time. A sudden change of temperature after
some fixed preassigned T(t) again would not result in a discontinuity of x, but
only of dx/ dt; however, pressure depends on T as well as on x (when V. is held
constant), and thus such a sudden change of temperature will result in a sudden
change of pressure. We would thus finally conclude that the constitutive equation
for pressure has the following form:
with the dependency on both v.(t - s) and T( t - s) having the fading memory
property.
We note that the ordered pair v.,
T would be identified as the site a.
Therefore, equation (5.1.7) suggests that the state of our system is
(5.1.9)
where nT is the total number of moles in the system. As the chemical reaction
proceeds, nT changes in time, which is obviously the reason why p depends on
x (this would not be true, of course, for an equimolar reaction, and therefore
the discussion here applies to a nonequimolar reaction). At equilibrium, the value
of nT would depend on temperature and on total volume. Therefore one would
conclude that the equilibrium pressure is given by an equation of the type
with f( .) nonlinear in both T and 1/ v" in spite of the fact that the mixture
behaves as an ideal gas at any given composition.
Let f3 be defined as follows:
(5.1.11)
(5.1.1l)
Appendix
We consider the more general case where the gas can still be regarded as
ideal, but the kinetics are not described by the simple linear expression in equation
S.1.2. Here
dx/ dt = r( v" T, x) (5.I.A.I)
Suppose x has been so chosen that its initial value is zero. Then the total
number of moles at any time is related to the initial value by
(S.I.A.2)
(5.I.A.5)
P+ (JdP/dt = 0 (S.I.A.S)
P = T + p1 = 2p. D (!I.l.A.!)
where P is called the extra stress (for an incompressible fluid, pressure is defined
only to within an arbitrary additive constant, and hence only the extra stress is
determined by its constitutive equation). The Maxwell equation is
P+ (JSP/St = 2p.D (!I.I.A.IO)
endowed with the fading memory property. The site a is the ordered pair (or
vector) V, T.
The first question to address is the mathematical formalization of the concept
of fading memory. This can be accomplished as follows. First, the space of
possible past histories of the site (i.e., of functions mapping the positive quantity
t - s into the ordered pair V, T) is assigned a topology such that two histories
which differ only in the distant past are close to each other. Second, the functionals
mapping the state into the. values of the constitutive quantities are assumed to
be smooth with respect to such a topology. This guarantees that the theory will
deliver values of the constitutive quantities which are close to each other for two
such histories. In the Appendix to Section 3.6, the concepts of topology, norm,
and metric have been introduced; however, they are not crucial to the theory of
continuous mixtures, where a norm of the simple type
The function a'(s) maps the time elapsed since a given site was imposed into
that site: It indicates how long ago that site was imposed. The domain of a'(s)
is the set of all positive real numbers; zero is not included, since a'(O) is simply
the present site a(t). which appears explicitly in the expression of the state. The
quantity a'(s) is called the history of the site at time t.
The free energy is given by an equation of the form
where the partial derivative is the ordered pair of partial derivatives with respect
to V and T, while the second term on the right-hand side is the Frechet differential,
the mathematical nature of which has been discussed in the Appendix to Section
3.6. Which particular Frechet differential is involved here is discussed at the end
of this section.
The partial derivative is of course to be understood in the sense that the
history is being kept constant. This can only be achieved by an instantaneous
change of site (albeit a differential one), but, as was discussed in the previous
section, such instantaneous changes do indeed make sense. (They would not
144 make sense for a viscous system, because a", which is included in the state for
viscous systems, would be infinite at such a change. In this sense, the theories
Chapter Five
of viscous and relaxational systems are seen to be mutually exclusive.) The Frechet
differential is to be understood as the initial rate of change of free energy which
would be observed should the site be held constant at the instant of observation.
This shows that 80{ } describes an essential feature of the behavior of relaxa-
tional systems.
If equation (5.2.7) is substituted in the second law, one obtains the results
p = -ao/av (5.2.8)
s = -ao/aT (5.2.9)
80:s 0 (5.2.10)
Equation (5.2.10) shows that the Frechet differential is indeed minus the
rate of energy dissipation. It also implies that, if volume and temperature are
held constant, free energy can only decrease in time-and hence that of all states
corresponding to an assigned site, the equilibrium state has the lowest free energy.
We note that the partial derivatives on the' right-hand side of equations
(5.2.8) and (5.2.9) are themselves functionals of the state, and therefore both
pressure and entropy are expected to change in time even if the site is held
constant; in other words, the equations give the instantaneous values of entropy
and pressure, which need not be equilibrium values.
The Frechet differential has been introduced in the Appendix to Section 3.6.
In the special case of the free energy functional, if the site is being held constant,
one can write
af+df(s) = af(s) + (aaf(s)/at) dt (5.2.11)
with the prime on the right-hand side indicating the ordinary derivative. Thus
the Frechet differential for the free energy functional in equation (5.2.10) is
with (!]'{ } being the functional derivative of the free energy functional.
5.3. EQUILIBRIUM AND DISSIPATION IN 145
RELAXATIONAL SYSTEMS
Thermodynamics
of Relaxation
It was a past that kept changing while he advanced in his trip,
because the traveler's past changes according to the path
followed, and I don't say only the recent past to which each
passing day adds a new day, but also the distant past.
I. Calvino
The history a'*(s) corresponds to the situation where the site has always been
held constant in the past at its present value, and therefore it obviously corre-
sponds to equilibrium. Hence the eqUilibrium values of all constitutive properties,
identified with an asterisk, are given by equations of the form'
However, one can never in actual fact know that the site has always been
kept constant in the past: what can be realized experimentally is only to keep
the site constant for a sufficiently long time. This situation can be described
mathematically as follows. Let a'(s) be the (possibly unknown) history of the
site at the time when one begins holding the site constant. At some later time T,
the history is
Such a history is called the static continuation of the history a' (s ). It is seen
that, as T - t increases, the distance between the static continuation and the
equilibrium history a'*(s) decreases. Thus the assumptions of smoothness for
the constitutive functionals guarantee that indeed equilibrium will be approached
asymptotically in static continuations.
Since a'*(s) is uniquely determined by the present site, the equilibrium
properties are unique functions of the site. Furthermore, in view of equations
(5.2.8) and (5.2.9), one concludes that the relationships between equilibrium
properties are the same as would apply for an elastic system. In this sense, it is
concluded that as long as one is only interested in the determination of equilibrium
properties, one can regard a relaxational system as elastic.
The rate of dissipation in relaxational systems is simply minus the Frechet
differential in equation (5.2.13). At any given instant in time of any transforma-
tion, one could start holding the site constant, and the free energy would begin
decreasing at a rate given by that Frechet differential. This gives a physical
146 interpretation of the dissipation rate in relaxational systems: it is the initial rate
Chapter Five
at which free energy would decrease should the site suddenly be held constant.
An important question to be addressed is the fOllowing: Is it possible to
perform a transformation in a relaxational system slowly enough to make the
total dissipation as small as one wishes? The answer, as shown below, is a quali-
fied yes.
Given a transformation a = lR(t), the history of the site at anyone time is
determined:
a'(s) = lR(t - s) (5.3A)
Now suppose that another transformation is accomplished, which scans the same
sites but at a slower rate. Such a transformation is called a retardation of the
original one, and the corresponding history of the site is
and
(5.3.8)
i.e., the second term is minus the instantaneous rate of change of the site in the
retarded transformation. Thus one obtains
The latter equation shows that, provided q is small enough (i.e., provided
the transformation is slow enough), a viscous theory is recovered asymptotically.
Since for viscous systems the total dissipation can be made as small as one wishes
by effecting the transformation slowly enough, the result has been proved.
The above analysis could be extended by retaining higher-order terms. This
would produce a series of higher- and higher-order approximations to the pressure
response for sufficiently slow transformations. In such a scheme, the elastic theory
(p = p*) is then identified as the zero-order approximation, the viscous theory
as a first-order approximation, and so on. Second-order constitutive equations
for the stress have frequently been used in the analysis of the deformation of
polymeric materials.
While the analysis given above provides proof that sufficiently smooth
transformations leading from one equilibrium state to another can be accom-
plished slowly enough to make the total dissipation as small as required, the 147
approximation procedure in higher- and higher-order constitutive equations is Thermodynamics
useful in practice only if the finite rate transformations to be analyzed are of Relaxation
reasonably well represented by a Taylor series truncated after a few terms for s
ranging from zero to some value well in excess of the relaxation time. For the
concrete case discussed in Section 5.1, volume and temperature changes would
need to be small and smooth over a time range of order () for any approximation
to be valid.
It may at first sight seem that the conclusion, that transformations in relaxa-
tional systems can be accomplished slowly enough to make the total dissipation
as small as required, is in contrast with the earlier conclusions, that the dissipation
connected with the occurrence of chemical reactions does not have that property.
However, the above conclusion is only that the dissipation can be made as small
as required if one starts from an equilibrium state, and indeed under such a
restriction the conclusion is valid for chemical reactions. However, in actual
practice the latter are not carried out starting from an equilibrium state, but the
reactants are simply brought together and allowed to react at whatever rate is
dictated by the kinetics of the reaction, and thus the total dissipation is necessarily
finite.
A final observation is in order. When developing a linear viscous theory, the
restriction imposed by the second law (the viscosity is to be nonnegative) is
somewhat intuitive, and thus the constitutive equation for pressure can easily be
expressed in a form which does not violate the second law. That is not the case
for relaxational systems, for which the restriction imposed is obtained by combin-
ing equations (5.2.8) and (5.2.10): the constitutive functional for pressure must
be expressible as the partial derivative of a constitutive functional for free energy
which enjoys the property in equation (5.2.10).
Since the equilibrium properties depend only on the site, equation (5.4.1)
implies that the internal energy of a system with entropic elasticity is always
equal to the equilibrium internal energy:
U = U* = u*(a) (SA.2)
The value of the functional in equation (5.4.3) represents the excess entropy in
non equilibrium states, and is zero at equilibrium.
The free energy is given by
The first two terms on the right-hand side cancel, because at eqUilibrium equation
(2.7.9) holds. The third and fourth terms cancel with the left-hand side, hence
as/aT = 0 (SA.(j)
i.e., the excess entropy is independent of the present temperature (but does
depend on the history of the temperature):
S = s*(a) + s{V; a'(s)} (SA.7)
p = p* + T as/ av (SA.8)
and, in view of equation (5.4.7), one concludes that the excess pressure p - p*
is proportional to absolute temperature. Rubbery solids are not elastic, since they
can dissipate mechanical energy, and in fact they are best described as relaxational
systems; however, they have entropic elasticity, and extra stresses are indeed
proportional to absolute temperature.
The second law for relaxational systems with entropic elasticity reduces to
This implies that, if the site is held constant, the entropy can never decrease, and
hence that of all states corresponding to any given site, the equilibrium state has
the largest entropy (the excess entropy is never positive).
It is possible to verify experimentally that a given polymeric system is indeed
endowed with entropic elasticity; in an adiabatic deformation it will heat up by
an amount corresponding to the total work done on it, and this can be checked. 149
Also, in an adiabatic stress relaxation experiment, temperature is predicted to
Thermodynamics
stay constant, and this can again be verified. Polymeric melts do in general exhibit of Relaxation
the predicted behavior.
A polymer melt undergoing deformation has, on the basis of the discussion
above, a lower entropy and hence a higher chemical potential than the same
polymer at rest. This is shown schematically in Figure 5.4.1, where the chemical
potential is plotted as a function of temperature at a constant pressure. The melt
at rest is represented by the lower curve on the right, and the melt undergoing
deformation by the upper curve at the right. The latter curve has a lower absolute
value of the slope, since the latter is in fact the entropy. The curve on the left
represents the free enthalpy of the solid; its intersection with the lower melt curve
identifies the eqUilibrium crystallization temperature TM. The curve for the melt
undergoing deformation intersects the solid curve at a temperature TJ > TM : as
a result, a polymer melt may crystallize at a temperature exceeding the equilibrium
one. This phenomenon of flow-induced crystallization has been observed experi-
mentally in polymer melts and in polymer solutions.
The dashed curve in Figure 5.4.1 represents the free enthalpy of a crystalline
form (II) other than that (I) of the full curve on the left. It should be noted that,
if the melt is at rest, when T > TM the liquid is the equilibrium phase; when
T < TM, the crystalline form I is the equilibrium one, and therefore the melt will
crystallize to form I-there is never a driving force for formation of the type-II
crystal. However, when the melt is undergoing deformation, if the temperature
is between TJ and T2 , a driving force for the formation of the type-II crystal
exists, and therefore the melt may indeed solidify into type-II crystals. At tem-
peratures lower than T3 , there is a driving force for a solid-solid phase transi-
tion from type-II to type-I crystals; however, solid-solid phase transitions are
extremely slow in polymers, in fact so slow that to all practical purposes one can
regard them as not taking place at all. It follows that, if indeed the melt has
solidified into type-II crystals, these will then be stable when cooled. Indeed, the
flowing melt
quiescent
FIGURE 5.4.1. Illustration of the phe- melt
nomenon of flow-induced crystalliza-
tion in a polymer. Crystalline form II
would never be observed in crystalliz-
ation from a quiescent melt. T
150 crystalline form obtained by flow-induced crystallization of polymers is often
Chapter Five
different from that obtained by solidification of the quiescent melt.
(5.5.1)
which does not admit discontinuous solutions. This was observed as long ago as
1901 by Duhem, who introduced the concept of a quasi-wave, a region of very
steep gradients but no discontinuity. In effect, while the Navier-Stokes equations
of classical fluid mechanics indeed do not allow for discontinuities, it is not true
that any dissipative theory (not even any linear one) smoothes out discontinuities.
The equation for a flexible string with linear friction has a structure which, in
terms of pressure and density, could be written as
(5.5.4)
Examples
1. Consider a mixture of two optical isomers A and B, and suppose that it behaves
as an ideal gas. Since the isomerization reaction is equimolar, volume has no influence
on the eqUilibrium composition. Furthermore, since the total number of moles is indepen-
dent of composition, so is pressure, and hence as long as only pressure is measured the
observed behavior is indistinguishable from that of a pure component. Suppose, however,
that the polarizability m is measured; this does depend on composition.
We choose a basis of one mole of A + B, and we define the extent of reaction as the
number of moles of B, so that 0 s x s 1. The equilibrium condition is
x"/(l- x*) = K(T) (5.E.I)
and assuming that the kinetics of the isomerization reaction is of mass action type
dx/ dt = k(1 - x) - kx/ K = (kx*)(x* - x) = F(T)[K(T) - x] (5.E.2)
where f( T) = 1/ F( T). Equations (5.E.2) is of the same form as equation (5.1.15). If one
makes the (quite reasonable) assumption that m is a linear function of X, a similar equation
will apply to m as well, i.e., the mixture will exhibit relaxation behavior, as far as the
polarizability is concerned, in response to variations of temperature.
Problems
5.1. A box of variable volume V initially contains I mole of component A. Component A may
dissociate according te,
A=2B
(the nitrogen oxide case discussed in Chapter 11 is a good example). Temperature is held constant 153
at all times. The following assumptions are justified:
Thermodynamics
I. The gas in the box is ideal. of Relaxation
2. The activity-based equilibrium constant of the reaction is unity.
3. The reaction is regulated by mass action kinetics.
a. Define an extent of reaction x such that its value is zero at time zero and its maximum possible
value is I.
b. Determine the value of the equilibrium extent of reaction x* = x*( V, T).
c. Determine the value of the equilibrium pressure,p* = p*( V, T). What is the value you calculate
when V approaches infinity? Explain.
d. Express the kinetics as dx/dt = reV, T,x).
e. Express pressure as p = f( v, T, x).
f. Eliminate x between the results in (d) and (e) to obtain a differential equation for pressure.
This equation may contain, of course, time derivatives of p and of V, but it should not contain x.
LITERATURE
SURFACE THERMODYNAMICS
NOTATION
Subscripts
L Liquid
G Gas
S Solid
t Total
1 Phase 1
2 Phase 2
Superscripts
I. Surface
I Phase I
II Phase II
Substantial time derivative
6.1. SURFACE TENSION
That such pygmies should cast such giant shadows only shows
how late in the day it has become.
L. Chatgaft
One is now tempted to generalize the definition of the state of, say, the liquid
phase by including the surface area among the external state variables, for
instance, to write a constitutive equation for free energy as follows:
The mass per unit interface area of an element located between n and
n+dnis
The free energy in the surface layer is different from (and, in view of Figure
4.1.1, larger than) that of phase 1. If one is willing to assume that the a( V)
function is the appropriate constitutive equation for free energy also in the surface
layer, the free energy per unit area, A~, is calculated as
and the total free energy of the two-phase system is thus given by
The important point is that the quantity A~ may depend on temperature and
pressure, but not on the interface area l: itself. In other words, the fact that free
energy is an absolutely additive function of mass guarantees that, insofar as it
may depend on interface area, it does so linearly.
One can now go through the usual argument, and conclude that in fact the
surface tension is the derivative of free energy with respect to l::
s = aa,/al: = A~ (6.1.7)
LIQUID GAS
(6.1.8)
We consider a liquid phase in contact with both a gas phase and a solid
phase (such as a liquid drop on a solid plate), and let the solid surface be plane.
As can be seen from Figure 6.1.1, a contact angle c/J can be identified. At
equilibrium, the contact angle is given by
(6.1.9)
Angle c/J can be both larger and smaller than 90°, according to the relative
magnitude of the solid-gas and solid-liquid surface tensions. When c/J > 90°, the
liquid is said to wet the solid. If a capillary is inserted vertically into a pool of
stagnant liquid, if the liquid wets the capillary it will rise to reach an equilibrium
height where the capillary pressure is balanced by gravity; if it does not wet the
capillary, it will dip to a depth determined by the same condition. If a capillary
is inserted horizontally into a liquid pool, a wetting liquid will move indefinitely,
if at a progressively lower rate, into the capillary.
Now we consider a liquid drop (phase 1) floating on the surface of another
liquid (phase 2); see Figure 6.1.2. At equilibrium, the following relationship
applies:
(6.1.10)
(6.1.11)
If condition. (6.1.11) is not satisfied, the drop will tend to spread indefinitely
on the surface of liquid 2. In actual fact, the spreading is not indefinite: As the
thickness of the surface film approaches that of a molecular monolayer, the
tendency to spread out disappears (this was observed by Benjamin Franklin, who
allowed a drop of olive oil to spread over the surface of the Clapham Common
pond in 1765. The final thickness was calculated at about 2.5 x 10-9 m, which is
close to the molecular dimensions of olive oil).·
GAS
(6.1.12)
df=s·dl (6.1.13)
s = s*1 (6.1.14)
(6.1.15)
d = !(divv)1 (6.1.16)
(6.1.17)
The quantity in square brackets could be regarded as a dynamic surface 161
tension, and it is seen to coincide with the equilibrium surface tension only if Surface
the rate of dilatation is zero. The second law imposes the following requirement: Thermodynamics
(6.1.18)
i.e., the work done on the system when the interface area is being increased is
no less, and may be more, than the work the system does when the interface is
being decreased. There is no analog of the Stokes hypothesis that the left-hand
side of equation (6.1.18) may be zero; indeed, finite values of it have been
measured.
Now consider a pure shear motion of the interface, say one where div v = O.
The surface tension tensor is now given by
(6.1.20)
and is thus nonzero whenever the surface tension is not constant over the interface.
When grad s is nonzero, the tangential stress at the interface must be nonzero in
at least one of the two phases. Since a fluid cannot sustain a tangential stress at
equilibrium, when grad s is nonzero at least one of the fluid phases will be set
in motion.
The surface tension may be nonuniform over the surface because of several
reasons, the two fundamental ones being as follows. The first is when temperature
is nonuniform; the corresponding motion is called thermo capillary motion. The
second is when concentration is nonuniform on the interface; as may well be the
case during mass transfer phenomena; the corresponding motion is called the
Marangoni effect.
162 6.2. SURFACE PHENOMENA IN MIXTURES
Chapter Six
Certainly, one is building on an insecure foundation, who rests
his work on hypotheses concerning the constitution of matter.
Difficulties of this kind have deterred the author from
attempting to explain the mysteries of nature, and have forced
him to be contented with the more modest aim of deducing
some of the most obvious propositions. ... The only error into
which one can fall, is the want of agreement between the
premises and the conclusions, and this, with care, one may
hope, in the main, to avoid.
J. E. Gibbs
(6.2.1)
where nl: is the vector of the number of moles at the surface. The whole analysis
is developed by assuming that
(6.2.2)
so that all the results obtained previously for the bulk phases still hold. In
particular equation (4.2.4), which plays a crucial role in the establishment of the
phase eqUilibrium conditions, is still regarded as essentially valid because of
condition (6.2.2).
Equation (6.2.1) can be expressed in the equivalent form
(6.2.3)
which shows that there is a fundamental ambiguity in the meaning of the vector
nl:. Indeed, if equation (6.2.2) holds true, the left-hand side of equation (6.2.3)
is the difference between two large quantitites which are almost equal to each
other. It follows that any even very minor ambiguity in the choice of how many
total moles to assign to phase I and phase II results in a very major difference
in the value of nl:.
The ambiguity can be resolved by a number of different arbitrary conventions.
The usual one is suggested by the considerations of dilute solutions, so that one
particular component (the solvent) plays a special role. Let 1 be the component
chosen as a reference. Furthermore, let I be the phase to which the surface layer
is attributed (usually the more dense phase, say the liquid in a gas-liquid system),
and let D be the operator defined as the difference between the quantity operated 163
upon in phase I and in phase II. Equation (6.2,3) can be rewritten as
Surface
Thermodynamics
(6.2.4)
which again has a value independent of the number of moles assigned to each
individual bulk phase.
Of course, different conventions could be used to define properly unam-
biguous surface properties, and such different conventions would of course result
in different values for the surface quantities. It is therefore important to keep in
mind that, although the equilibrium surface tension is still the partial derivative
of the total free energy with respect to interface area, it is not equal to Al:, except
for one particular convention which is not the one usually adopted. Indeed,
chemical potentials at the interface can be defined as follows:
(6.2.9)
which can be shown to be independent of the convention used [both Al: and r
depend on the convention chosen, but the derivative in equation (6.2.9) does
not]. Some cumbersome algebra, which essentially duplicates that relative to
mixtures discussed in Section 3.3, yields the following equilibrium results:
s=Al:-r·"l: (6.2.10)
r = -as/a"l: (6.2.11)
Equations (6.2.11) and (6.2.12) together afford a means of measuring the relative
adsorptions at the interface.
164 It is important to realize that, in the case of mixtures, there are in fact two
types of phenomena which may result in non-equilbrium surface properties. The
Chapter Six
first type is connected wit~ the actual possibility of motion of the interface, and
is thus of the same type as discussed in the previous section. The second type is
connected with the fact that, as new interface area is formed, it may well in
general form at a composition quite different from that at equilibrium. This in
turn implies that equilibration now requires individual components to diffuse
toward or from the interface, a process which may well be rather slow; of course,
as long as the interface composition is different from the equilibrium one, so are
all other surface properties. This is particularly relevant in the case of solids,
where diffusion from and to the interface may be extremely slow, so that the
actual surface composition may differ from the equilibrium one for substantial
lengths of time. The catalytic properties of solid surfaces are strictly related to
this type of phenomenon.
Appendix
c
50lvent
solute
5 pOSition n
the sum of all areas on the right equals the sum on the left. In addition, one 165
could use mass units rather than mole units, and this selection entails a whole
Surface
new series of possible choices for the arbitrary position of the "equivalent Thermodynamics
surface."
Problems
LITERATURE
DISSIPATIVE PHENOMENA
NOTATION
A Constant parameter
At Total free energy kcal
a Constant parameter kmolm- I S-I
a "Thermodynamic coordinate"
B Constant parameter K- 1
b Arbitrary vector
b Constant parameter kmolm- 3 s- 1
c Concentration vector kmolm- 3
Cv Constant volume specific heat kcal kmol- I K- 1
D (Section 7.3) Diflusivity matrix m2 s- 1
D (Section 7.4) Rate of deformation tensor 8- 1
Subscripts
j, k For component j, k
SS Steady state
Superscripts
+ Symmetric part
Antisymmetric part
* Talandic
T Transpose
Substantial time derivative
7.1. HEAT TRANSFER
[We shall see in more detail in Section 7.5 that the second law reduces to the
requirement in equation (7.1.1) only for steady-state phenomena. In other words,
for unsteady-state phenomena, the second law does not forbid heat to flow in
the direction of increasing temperature, if only for short intervals of time.]
At equilibrium, temperature is uniform in space (Le., grad T = 0), and there
is no heat flux. It is therefore reasonable to assume that the heat flux vector
depends on the temperature gradient. The heat flux is a function of state, and
thus the simplest possible form of constitutive equation for it is
q = q(grad T, V, T) (7.1.2)
This, however, implies that the state is {grad T, V, T}, and hence one would need
to assume that all functions of state depend on grad T. With this assumption, the
second law reduces to
q = -Kograd T (7.1.6)
where K is the conductivity tensor. Any tensor can be decomposed into the sum
of a symmetric and an antisymmetric tensor:
and (7.1.7)
(7.1.8)
which has caused a great deal of discussion in the technical literature is whether
K is necessarily symmetrical for all solids or not. According to the so-called
thermodynamics of irreversible processes (hereafter referred to as TIP), K is
necessarily symmetric. However, this conclusion is debatable, as discussed below.
First of all, if temperatures are prescribed on the bounding surface of the 173
body considered, the resultant temperature distribution will depend only on the
Dissipative
symmetric part of K, and hence no experiment of this type could settle the issue. Phenomena
However, experiments could be carried out where boundary conditions are
imposed on the heat flux rather than on temperature itself (for instance, some
part of the bounding surface could be kept adiabatic), and therefore the issue
could in principle be resolved by experiment. However, there are several experi-
mental difficulties. First, the solid should not be a randomly microcrystalline one,
which would be macroscopically isotropic, but should be macroscopically non-
isotropic, say ideally it should be a single crystal. Symmetries of single crystals
are well known, and for a large variety of crystalline classes the symmetry of K
is simply a consequence of the symmetries of the crystal; however, for some
crystals (like gypsum, erythrite, dolomite, etc.) this is not so. Stokes laid down
the hypothesis that indeed K is symmetric, i.e., that K- = 0, and in fact he wrote
that "it is only among crystals which possess a peculiar sort of asymmetry, that
we should expect to find traces of [its] existence." Very few experiments which
could yield an answer have been performed, and these seem to indicate that
indeed K- = 0; however, there is no thermodynamic reason why it should
necessarily be so for all solids.
While for the case of single crystals the question of whether the conductivity
tensor is or is not necessarily symmetric may seem rather academic, that is not
so in the case of polymers. Polymers, even if isotropic when at rest, may well be
anisotropic when flowing, as evidenced by their exhibiting flow birefringence.
Whether this anisotropy has any effect on the heat transfer in polymers is not
known; it is however potentially of importance, because heat transfer in flowing
polymers occurs in almost all polymer processing operations.
7.2. HYDROSTATICS
(7.2.3)
We note that, when the chemical potential has the hydrostatic distribution,
no mass flux will occur, in spite of the fact that the gradient of chemical potential
is not zero. This point will be discussed in more detail in the next section.
The result in equation (7.2.3) is in fact not restricted to ideal gases. The
hydrostatic pressure distribution is given in general by
M=M·y (7.2.6)
where M is the molecular weight vector, the components of which are the
molecular weights of the individual components.
A philosophical problem arises at this stage. There are in fact two distinct
possibilities: the first is to assume that equation (7.2.5) holds for the free enthalpy
of the mixture, say
In the next section, a proof is given that indeed equation (7.2.8), rather than
equation (7.2.7), is the correct one for mixtures.
It is now useful to define the matrix P G as follows:
P G = 8p./8y (7.2.9)
P~'y = 0 (7.2.10)
y-[PG·(dy/dh)] =0 (7.2.13)
dy/dh·(P~·y) = 0 (7.2.14)
(7.2.15)
Since partial molar volumes and average molar volumes are of the same order
of magnitude, the right-hand side is of the order of a molecular weight difference
8M times the gravity acceleration. For an ideal solution, the baric derivative of
the chemical potential with respect to the mole fraction is RT. For nonideal
solution that is of course not true, but for the purpose of an order of magnitude
analysis RT is still a good estimate. One thus concludes that X satisfies
X ""2RT/g8M (7.2.16)
176 At room temperature, 2RT/g is about 5 x lOSmkgkmol- l • Therefore, even
with 3M values of order 100 kg kmol-I, the significant length scale is of the order
Chapter Seven
of a few kilometers. One may thus conclude that, except for special cases (like
the distribution of composition in the atmosphere or iIi deep oil wells), the
hydrostatic effect can be negected altogether, and the equilibrium distribution of
chemical potentials is uniform in space.
7.3. DIFFUSION
Since the tum of the century anyone who has set pen to paper
in an attempt to advance thermodynamics has come under
attack from one quarter or another, and the only thing upon
which we all agree is that Gibbs was a very smart fellow. So,
not knowing what to make of the battles raging around us, we
, opt for neutrality: we confine our teaching to the substance and
style of 19th century thermodynamics. Although this course of
action has served us reasonably well and, incidentally, lends to
the subject an undeniable charm, at some point we must ask if
such a state of affairs is to prevail forever.
M. Feinberg
The nonequilibrium theory of mixtures is remarkably complex, and only a
conceptual sketch will be given here. The complexity is twofold: conceptual and
mathematical. Therefore, in order not to cloud the conceptual issues involved,
attention is restricted to a geometrically very simple case.
The conceptual difficulties are related to two problems, which are connected
with each other. The first problem is the following one. In a mixture where
diffusion occurs, the components are in relative motion with each other, and so
there is some ambiguity about what is meant by the average velocity of the mixture
as a whole. As will be discussed below, this ambiguity can in fact be resolved,
based on the requirement that the equations of motion for the mixture as a whole
should be written in the usual form, say for a Newtonian fluid in the form of
the Navier-Stokes equations. 'However, when the ambiguity is resolved in this
way, the diffusive fluxes need to be defined in a way which is at odds with that
usually adopted in the theory of mass transfer.
The second problem is related to the fact that, in the presence of diffusive
phenomena, the concept of a body (as a closed system which does not exchange
matter with its surroundings) is in a sense lost: even if one considers the neighbor-
hood of a material point as in describing the motion of the mixture as a whole,
no matter how one allows such a neighborhood to deform in time, it still exchanges
matter with its surroundings. This implies that, when writing balance equations
(or trended imbalances like the second law) in the Lagrangian form (Le., with
substantial rather than partial time derivatives), one still has to take into account
convective fluxes. Indeed, the literature rooted in mechanics chooses to regard
what chemical engineers would consider convective fluxes as conductive fluxes,
so as to retain the characteristic that, in the Lagrangian form of balance equations,
only conductive fluxes are involved.
The simplifications introduced are as follows. First, a one-dimensional prob-
lem is considered, Le., all quantities are regarded as variable only along one
direction, say z, Second, temperature is assumed to be uniform in space. Third, 177
some of the conceptual points are discussed by restricting attention to two special
Dissipative
cases: a binary mixture of ideal gases, and a binary liquid mixture the density Phenomena
of which is independent of composition. Finally, at the end of the analysis the
further simplification of considering only steady-state phenomena is made.
Let us consider first the very simple case of a one-component system moving
at some velocity v(z) (if v indeed varies along z, the density needs to be changing
in time). The mass flux Q', i.e., the mass crossing the plane orthogonal to z at z
per unit area and per unit time, is simply the product of the density times the
velocity, Q' = cl>v. The molar flux N' is of course simply Q'/ M, with M the
molecular weight. Of course, one would not regard Q' or N' as manifestations
of what we intend by diffusion: they simply represent the actual motion of the
system.
The next step is to consider a mixture which moves as the single component
considered above, with nothing else happening. In other words, all the com-
ponents of the mixture move with the same velocity. The mass of component j
per unit volume of the mixture, cl>j' is
(7.3.1)
where Wj is the weight fraction (the values of Wj naturally sum to unity). Thus
one calculates the fluxes:
and (7.3.2)
where cj = cl>wj/ ~ is the concentration of the jth component. The total mass
flux is
N' = L N; = v L cj (7.3.4)
Again, one would not regard these fluxes as being diffusive fluxes, since they
simply reflect the motion of the mixture as a whole.
Diffusive fluxes arise when the individual components move with different
velocities. Let Vj be the velocity of component j; one has
(7.3.5)
(7.3.6)
The diffusive mass flux of component j is the difference between its actual
mass flux and the flux it would exhibit if the mixture simply moved as a whole,
say
(7.3.7)
178 and of course the diffusive mass fluxes add up to zero. The quantities Uj are the
relative diffusion velo«ities.
Chapter Seven
The molar fluxes are
(7.3.8)
(7.3.9)
We note that while the quantities Qj sum to zero, the ~ do not. In order to
understand this point, consider a binary liquid mixture the density of which is
independent of composition. Let such a mixture rest in a long cylinder with
sealed ends, with diffusive fluxes taking place. Since density is constant, no net
mass flux takes place, and hence v = o. The two mass fluxes must necessarily be
equal and opposite to each other. However, the total molar flux is not zero, since
the two molar fluxes will be in inverse proportion to their molecular weight.
The point discussed· above is related to the interpretation of the velocity of
the mixture as in equation (7.3.6), i.e., as the mass-average velocity. Of course,
one could have chosen the alternate approach, say one could regard the molar-
average velocity as the velocity of the mixture as a whole:
(7.3.10)
in which case the molar diffusive fluxes would add up to zero but the mass
diffusive fluxes would not.
For this case it is useful to consider a binary mixture of ideal gases in a long
cylinder with sealed ends, with pressure constant along z. Since the molar density
of an ideal gas at constant temperature and pressure is independent of composi-
tion, the net molar flux is zero in such a system, say now v' = 0; the two molar
fluxes are necessarily equal and opposite (this is called equimolar counterdiffusion
in classical mass transfer theory). However, the mass flux is not zero, since mass
would actually move in the direction in which the heavier component is diffusing.
Hence, from a mass viewpoint, the mixture would actually be moving.
The substantial time derivative of any quantity L is, for the simple geometry
considered here,
and it represents the rate of change observed as one moves together with the
mixture as a whole. Therefore, any ambiguity with respect to what is meant by
the velocity of the mixture as a whole results in an ambiguity in what is meant
by the substantial time derivative.
The ambiguity in fact must be resolved in favor ofthe mass average velocity,
since the equations of motion for the mixture as a whole must have the same
form as they would for a single-component system. Let us consider, for example,
the case of classical fluid mechanics, where the Navier-Stokes equations are
regarded as correctly describing the flow behavior of the fluid, independently of
whether the fluid is a single-component one or a mixture. The density appearing
in the Navier-Stokes equations is undoubtedly the mass density, not the molar
density, and therefore the velocity appearing in them is the mass-average velocity. 179
It is of course still perfectly legitimate to write the mass balance of each component Dissipative
in terms of molar fluxes, say cj = -a~/ az, but the ~ must be interpreted as in Phenomena
equation (7.3.9), and not as Cj(Vj - v'), and consequently they will not add up
to zero. In the following, the analysis is carried out in terms of the mass fluxes,
and only the final results are recast also in terms of the molar fluxes, to be
interpreted in the sense of equation (7.3.9).
If one wishes to express the relevant equations in terms of mass fluxes, it is
necessary to consider partial mass properties, as distinguished from partial molar
properties. Since the whole matter of partial molar properties is simply related
to the fact that extensive properties are absolutely additive functions of mass,
partial mass properties are legitimate, and in particular all the relationships
holding for partial molar properties apply to partial mass ones as well. The
notation L" will be used for partial mass properties. Also, the density of any
extensive quantity L is to be understood as the mass density, not the molar density.
Now consider the first law as it applies to our system. In particular, suppose
that the frame of reference has been chosen so that v = 0, uj = Vj; it follows that
the partial derivatives coincide with substantial derivatives in the usual sense. It
is easiest to follow the argument by having in the back of one's mind the picture
of a liquid mixture in a long cylinder sealed at the ends, with density being
independent of composition, so that in fact the actual net mass flux is zero. With
this, substantial derivatives are simply partial derivatives with respect to time in
the frame of reference fixed to the cylinder walls. We consider a differential
volume between two unit area planes orthogonal to z separated by a distance
dz. This is of course an open system, into which energy can flow not only by
heating and by work, but also by convection of energy. Indeed, the flux of energy
in the positive z direction equals the sum of the flow of heat, the rate of work
being done, the convective flux of internal energy, and the convective flux of
kinetic energy, and therefore the first law is
where q is the heat flux in the positive z direction, which may be nonzero in
spite of temperature being constant since coupling of diffusion and heat transfer
may occur.
If, as is usual in the mechanics literature, one wants to retain the fact that
in a Lagrangian formulation only conductive fluxes appear, equation (7.3.12) is
to be interpreted in the sense that, in a mixture, the conductive flow of heat is
q + I (Uj + !uJ)Qj. This may at first sight appear as very artificial, but in actual
fact it is not. Indeed, in the Maxwellian kinetic theory of gases, the heat flux is
by definition the flux of kinetic energy, say it is the equivalent of the uJ term in
equation (7.3.12).
The work term is calculated as follows. Let us consider componentj entering
the system at z, and let (PJ be its volume fraction. The pressure is p, but the
component only crosses a fraction CPj of the unit cross-sectional area, and hence
the force is PCPj, and the rate at which the component is doing work on the system
is PCPjVj. The velocity is in fact Qj/~j; see equation (7.3.5). The ratio CPj/~j is
recognized to be the volume of component j per unit mass of the same component,
180 Le., it is in fact the partial mass volume. Therefore the net rate of work is given
by
Chapler Seven
Had one chosen to write the equations in terms of the molar fluxes, the
density appearing on the left-hand side of equation (7.3.14) would have been the
molar density. The latter would depend on composition in a constant-density
liquid; conversely, in a mixture of ideal gases the molar density is independent
of composition but the mass density is not.
We now turn our attention to the second law. There are again two mechanisms
for the flow of entropy j, namely,
(7.3.15)
and, in the absence of radiant heat, the second law can be written as
where
(7.3.20)
The usual assumption of smoothness near equilibrium now implies that at equi- 181
librium (i.e., when the diffusive fluxes are zero) the 4>; are uniform in space.
Dissipative
When the diffusive are also zero, the kinetic energies of diffusion are also zero, Phenomena
and hence one recovers the conclusion that the chemical potential has the
hydrostatic distribution at equilibrium. The assumption of smoothness near
equilibrium can also be used to yield a linear constitutive equation for the fluxes:
(7.3.21)
(7.3.22)
where
The quantity JLj + ~gh is seen to be the difference between the actual
chemical potential and the value it would have under hydrostatic conditions. The
simplest way of dealing with the unusual term ~gh is to simply redefine the
chemical potential as JLj + ~gh, so that gravitational effects are automatically
taken into account (but see the Appendix in this regard). It is perhaps surprising
that, even with this redefinition, the chemical potential is not the potential for
diffusion, because of the uJ term appearing in equation (7.3.23).
The kinetic energies of diffusion are almost always very small, and if they
are neglected the chemical potential is indeed the potential for diffusion. It is
seen that equation (7.3.20) does not require every diffusive flux to be in the
direction of decreasing chemical potential, i.e., coupling between diffusive fluxes
is possible, and they are indeed observed experimentally. In the case of diffusion,
coupling must always be taken into account, since it is not possible to have only
one chemical potential nonuniform in space.
Let N be the molar flux vector (i.e., the vector whose components are the
fluxes of the N components of the mixture in the z direction) and L be the matrix
whose components are Ljk • Equation (7.3.22) can be written in the form
N = L·d,../dz (7.3.24)
Appendix
The question of whether one should regard I-' or I-' + Mgh as the chemical
potential is not simply a matter of taste. If one wants to regard the chemical
potential as a function of state, then it cannot include the term Mgh, since the
latter is defined only in reference to an externally imposed gravitational field
which is not a legitimate state variable. Let us consider one gram of air at 20°C
contained in a one-liter box; its chemical potential is expected to be the same
whether the box is on the Earth or on the Moon-thus one should not, in principle,
callI-' + Mgh the chemical potential. In the Maxwellian theory of gases, one can
formally add a gravitational term to the Hamiltonian, and the resulting chemical
potential will in fact be uniform in space at equilibrium, since itreally is I-' + Mgh.
However, this is only formal; in substance, the Hamiltonian should only depend
on properties of the collection of particles considered, and therefore it should
not contain a gravitational term.
7.4. MOMENTUM TRANSFER 183
Dissipative
... when different strata of a gas slide upon one another with
Phenomena
different velocities, they act upon one another with a tangential
force tending to prevent this sliding, and similar in its results to
the friction between two solid sUrfaces sliding over each other
in the same way. The explanation of gaseous friction, according
to our hypothesis, is, that particles having the mean velocity of
translation belonging to one layer of gas, pass out into another
layer having a different velocity of translation, and by striking
against the particles of the second layer, exert upon it a
tangential force which constitutes the internal friction of the gas.
J. C. Maxwell
F = f(vlr) (7A.1)
with f(O) = o. This implies that vi r is to be regarded as a state variable, say the
state is
(The whole system is a square prism of unit cross-sectional area and height r.)
By reasoning analogous to that in Section 7.1 leading to the conclusion that
free energy cannot depend on the temperature gradient, it is now concluded
that for the case at hand it cannot depend on vI r. The free energy is still a
potential for entropy, and since pressure is constant in space the second law
reduces to
Since the total volume of the system is constant in time, one concludes that Fv
must be positive, say that the force F must point in the same direction as the
velocity v. If it is assumed that the f( . ) function in equation (7.4.1) is linear, the
proportionality constant is the viscosity of the fluid, and the second law requires
the latter to be nonnegative.
The discussion in the last paragraph was somewhat simplified, but in the
proper three-dimensional formulation the conclusions which can be rigorously
deduced are indeed those stated. The constitutive equation, which is the three-
dimensional analog of equation (7.4.1) in its linear form, is equation (2.3.A.l);
for an incompressible fluid, tr D is zero identically, and so the second term on
the right-hand side drops out. We note that an incompressible viscous fluid cannot
accumulate elastic energy, and hence all the net work done by contact forces is
dissipated. This is not necessarily so for all fluids, and viscoelastic fluids which
are capable of accumulating some elastic energy are known to exist. In this regard,
see Chapter S.
The linear relationship between stress T and the symmetric part of the velocity
gradient D implies only a scalar parameter, the viscosity. This is due to the fact
that requirements of invariance require the mapping of D into T to be isotropic.
Since every isotropic matrix is necessarily symmetrical (though of course not vice
versa), the question of the symmetry of the matrix appearing in the linearized
constitutive equations for momentum flux is disposed of by a requirement of
invariance.
It is important to realize that the requirement that Fv ~ 0 is only imposed
at steady state. Indeed, even in the Maxwellian theory of gases, equation (S.1.A.8)
applies, and hence if the gas is being sheared steadily in one direction, and at
time t the shearing direction is suddenly reversed, the tangential stress will, for
very short times, point in a direction opposite to that of shearing, say Fv < O.
7.5. UNSTEADY TRANSPORT 185
Dissipative
We are all agreed that your theory is crazy. The question which Phenomena
divides us is whether it is crazy enough to have a chance of
being correct. My own feeling is that it is not crazy enough.
N. Bohr, commenting on a paper presented by W. Pauli
(7.5.1)
For steady-s~e conditions, this implies that the heat flux vector forms an obtuse
angle with the temperature gradient; the simplest constitutive equation satisfying
this constraint is the isotropic form of Fourier's law with a positive heat conduc-
tivity Ie. Now consider unsteady-state conditions. If the body examined is also
undergoing deformation, one would have two parallel mechanisms ofirreversibil-
ity, and this will be discussed in the sections on coupling. Here we treat the case
where the body is stationary (or in rigid-body motion), so that w = 0, and the
first law reduces to
U'=q (7.5.2)
Should equation (2.7.13) apply, the first two terms in equation (7.5.1) would
cancel out; however, equation (2.7.13) does not necessarily apply when the system
is not at steady state, and hence the heat flux and the temperature gradient vectors
do not necessarily form an obtuse angle. (See the Appendix in this regard.)
Even if the isotropic form of Fourier's law has been established experi-
mentally for steady-state conditions, it need not hold also under unsteady-state
conditions. Indeed, consider the following constitutive equation for the heat flux,
analogous to the Maxwell equation for the stress discussed in Section 5.1:
with 8, the relaxation time for heat flux, a positive constant. This equation is
guaranteed to deliver a heat flux vector which, in steady state, forms an obtuse
angle with the temperature gradient vector, and its validity (or lack thereof)
cannot be ascertained by steady-state experiments.
At unsteady state, equation (7.5.3) does allow the heat flux vector to form
an acute angle with grad T, as the following simple example shows. Suppose
grad T has been held constant at some value, and correspondingly the heat flux
forms an obtuse angle with it. At some time t = 0, the temperature gradient is
suddenly reversed. The heat flux will also reverse in a time scale of order 8, but
186 at t larger than 0 by an amount negligibly small as compared to 8 it will still
Chapter Seven
have the direction it had at negative times-and hence it will form an acute angle
with grad T.
This, however, does not contradict the second law, since equation (7.1.3)
requires the heat flux to form an obtuse angle with grad T only at steady state.
If a finite relaxation time 8 is allowed for, the usual Maxwell relations do not
hold at unsteady state, and hence the othenerms appearing in equation (7.5.1)
may well compensate for a positive value of the last term on the left-hand side.
Indeed, some experimental results on the rate of crystallization in polymers
suggest that a constitutive equation for the heat flux of the type of equation
(7.5.3) is needed in order to model the data. From a microscopic viewpoint, one
could simply consider the possibility that, as a temperature gradient is suddenly
applied to the system, the morphology tends to undego some change with some
intrinsic kinetics dominated by a time scale of order 8; thus one would have a
relaxational system for the heat conduction phenomenon. Let us consider the
classical Maxwellian gas with u the molecular velocity with respect to the mixture
as a whole and (I) the average of any quantity lover the distribution function.
The heat flux vector is given by
(7.5.4)
where uu is the dyadic product. Since stress in a Maxwellian gas does exhibit
the phenomenon of relaxation [see equation (5.1.17)], so does the heat flux.
Indeed, the constitutive equation for the heat flux obtained from the theory of
the Maxwellian gas is significantly more complex than equation (7.5.3).
For the Maxwellian gas, the relaxation time for heat flux is ~ of that for
momentum flux, and it can be shown to be the largest possible of all relaxation
time scales. All such relaxation times are negligibly small for gases at ambient
conditions.
Appendix
If the density is constant, and one assumes the system to be elastic, then
any function of state depends only on T [say U = u(T), S = s(T), etc.]. It
follows that, since no work is done,
q/T = U·/T = cvT/T (7.5.A.I)
and
S" = (ds/dT)T = q/T (7.5.A.2)
and
where a is (t - t')/6, t being the instant of observation and t' any previous
instant. Since T depends on a, the two expressions above do not cancel out.
7.6. COUPLING
When more than one dissipative phenomenon is taking place there is always
a possibility of coupling, and the second law requires the total dissipation rate
to be nonnegative without restricting the individual ones. It is useful to distinguish
between two types of coupling, indirect and direct coupling; these are discussed
concisely in the following.
As an example of indirect coupling, consider the case of simultaneous heat
and momentum transfer. The usual way of dealing with such problems is to
assume that the constitutive equations which have been separately established
for the two transport phenomena when each is the only one taking place hold
also under conditions where the two take place simultaneously. This assumption
consists essentially in assuming that there is no direct coupling and, as will be
discussed later, it is an assumption which is not necessarily good, and is certainly
not dictated by the second law of thermodynamics. Nonetheless, even with such
an assumption, the two phenomena may still be coupled in an indirect way.
Indeed, some examples have already been considered explicitly: if temperature
is nonuniform on the interface between two fluid phases, a surface tension gradient
will induce thermo capillary motion in at least one of the two phases. Heat transfer
by free convection is another example of a flow induced by temperature differen-
ces, i.e., of an indirect coupling between heat and momentum transfer.
It is useful in this regard to consider the operation of a refrigeration cycle.
It is obvious that, on a macroscopic scale, heat flows from a cold source to a
hotter sink in a refrigerator: thus the idea that the second law requires heat to
invariably flow from hot to cold is belied by the fact that refrigerators do work.
In fact a refrigeration cycle can be analyzed on the basis of extremely simple
188 constitutive assumptions for the working fluid. In the discussion that follows,
reference is made to the classical Camot cycle analysis of a refrigeration cycle;
Chapter Seven
see Figure 7.6.1. The cycle starts at, say, point 1, where. the fluid is compressed
to some higher pressure. The fluid is regarded as bei~g an elastic gas, since
compression takes place sufficiently slowly that viscous effects can be neglected
(it should be borne in mind that viscous effects in compression and expansion
are negligible unless the rate of change of density is extremely high). Thus the
compression is reversible, and if it can regarded as adiabatic as well (which is
reasonable for sufficiently large units: as the size of the unit increases, its
surface-to-volume ratio decreases, and thus it approaches adiabatic behavior)
the compression will be isoentropic, thus resulting in the vertical segment 12 (in
Figure 7.6.1) of the Camot cycle. We note that here the characteristic of the
compression step (i.e., its being isoentropic) is deduced from the second law, by
making use of the independently arrived at conclusion that the step takes place
reversibly. The horizontal segment 23 corresponds to a change of phase taking
place at temperature T1 , again regarded as reversible. Here the fluid discharges
heat to the warm source, which in actual fact will be somewhat colder than TI
but which can in principle be at a temperature as close to TI as one wishes.
The segment 34 presents some subtlety. It corresponds to an expansion which
again can be regarded as adiabatic. It would therefore appear that one can again
regard it as isoentropic, but in fact it is generally assumed to be isoenthalpic if
it takes place through a nozzle valve. This is connected to the fact that expansion
through a valve is so sudden that viscous effects cannot be neglected, and therefore
the expansion is not reversible: indeed, the fluid does no work at all on the
surrounding if it expands through a nozzle valve. In this case, the characteristic
of the step (its being isoenthalpic) is deduced from the first law, by making use
of the fact that the fluid does no work on the surrounding. It is, however, possible
to effect the expansion not through a valve but through some kind of device such
that the fluid does do work on the surrounding, and expands slowly enough to
I Heat discharge
3
ExpanSionD
device
4 1
f Heat pickup
T1 ------02
T2 ------4
3
and, by an argument strictly analogous to that developed in Sections 2.4 (as far
as V'· is concerned) and 7.1 (as far as grad T is concerned), we can conclude
that free energy depends in fact only on V and T. It can also be concluded that
free energy is a potential for entropy, so that also the latter depends only on V
and T. However, free energy is not a potential for the heat flux, and it is a
potential only for the equilibrium pressure p* (corresponding to both V· and
grad T being zero) but not for the actual pressure p. The second law reduces to
It is seldom useful to write chemical kinetics in this way, but this is irrelevant
to the present discussion-a neighborhood of the eqUilibrium point exists where
equations (7.6.3) hold if indeed both affinities are zero at equilibrium, as was
discussed in Chapter 3. Now the second law requires that
(7.6.4)
These conditions certainly do not require k12 to be equal to ~1' and there is no
reason whatsoever to think it should be. (The argument could easily be generalized
by introducing a kinetic constant tensor with components klJ , and it would then
be exactly analogous to that developed in Section 7.1, with no crystal symmetry
available to be invoked for providing the appropriate symmetry.)
We now note that, if one makes the usual assumption in chemistry, i.e., that
the two terms on the left in equation (7.6.4) are separately nonpositive, one would
conclude that both k12 and k21 are zero, i.e., that the kinetic constant matrix is
diagonal. Since every diagonal matrix is symmetric (though the converse is not
true), one would obtain a stronger result than the symmetry asserted by TIP.
Thus two possibilities remain: either the system considered is simple enough for
the usual assumption in chemistry to hold, and then the matrix is not only
symmetric, but also diagonal; or the system is more complex than that, in which
case there is no reason to suppose it is symmetrical, but only that it is positive
definite.
J=L·X (7.7.1)
Z/T=J·X (7.7.2)
This is, however, not an acceptable definition, since infinitely many different
couples of vectors may well have the same scalar product. Indeed, let us consider
a new set of fluxes, J', given by
where W is any nonzero skew matrix. If L is symmetric, the vector J' is not related
to X by a symmetric matrix, since W is nonzero. Yet J' could well be taken as
the set of fluxes, since it satisfies equation (7.7.2). In fact, by an elementary
theorem of matrix algebra
(W·X)·X = 0 (7.7.4)
and therefore
Conversely, suppose sets J' and X are given for which L is not symmetrical.
Then L can be decomposed into its symmetrical part D and skew part W, and a
new set J can be defined as
where G is a (constant) symmetric matrix. The sets J and X are now defined as
J= a' (7.7.8)
and
X=G'a (7.7.9)
a = f J dt (7.7.10)
where a vector flux (order-one tensor) is coupled with the scalar (order-zero
tensor) quantity, temperature T.
It is generally a frustrating exercise to try to understand what statements in
the TIP literature really mean. However, equation (7.7.8) must have been formu-
lated by somebody who was thinking of chemical reactions; the flux would then
indeed be the rate of reaction, the thermodynamic coordinate the extent of
reaction, and the force the affinity. Of course, chemical kinetics are rarely linear,
but we shall forget about that for the time being. Chemical reactions do occur
often (if not invariably) in the presence of heat transfer, and so the question of
coupling between the two arises. At a given temperature gradient, mayor may
not the heat flux in a reacting mixture depend on the extent of reaction? This
seems to be the question addressed by TIP, and the answer, with the Curie
principle in either form, is no-the heat flux is a vector, and the extent of reaction
is a scalar. This conclusion is clearly nonsense, since the thermal conductivity of
a mixture may very well depend on composition, and thus on the extent of reaction.
An even more dramatic example is that of a polymerization reaction. As the
degree of polymerization increases, the viscosity increases by several orders of
magnitude and therefore, at an assigned value of the shear rate tensor, the stress
tensor changes dramatically. This would be forbidden by the Curie principle in
its strong form-though, admittedly, not in its weak form, since stress is a tensor
and the extent of reaction is a scalar, i.e., the orders differ by two.
Returning to the example of coupling between heat flux and extent of
reaction, one can convince oneself that the Curie principle is not only wrong, it
is meaningless. Let us consider a mixture in which three chemical reactions take
place simultaneously. Now the extent of reaction is a three-dimensional vector,
and according to the Curie theorem in such a case the heat flux could depend
on it. Does it make any sense to think that the heat flux can depend on the extent
of reaction vector only when there are exactly three independent reactions going
on? One could argue oneself out of this paradox by saying that by "vectors" one
means three-dimensional vectors in physical space, and not ordered triplets of
numbers, and that therefore the extent of reaction is not a vector. However, this
leads to another paradox. In fact, either the Curie principle is a theorem in
algebra, or it is a principle of physics. In algebra, the distinction between ordered 195
triplets of numbers and vectors in physical space disappears. So the Curie principle Dissipative
needs to be a principle in physics. From which fundamental laws of physics is Phenomena
it deduced?
Finally, it is of interest to observe that, if one undertakes the painstaking
exercise of following the Curie principles through the chain ofliterature references
in the TIP literature back to its origin, one does reach a work by Curie in which
nothing even remotely similar to the Curie principle is stated.
We now tum our attention to another difficult point in the literature on TIP,
which is the question of a vaguely formulated principle of minimum entropy
production. Again an unambiguous statement of the principle is hard to pin
down, but the following formulation is perhaps a reasonable synthesis of what
can be found in the literature:
"Given a dissipative phenomenon which takes place under conditions such
that all boundary conditions imposed on the system are steady-state ones, the
spatial distribution of variables is such as to result in the minimum global rate
of entropy production (or energy dissipation) compatible with the imposed
boundary conditions."
A trivial counterexample is easily found. Flow of a Newtonian fluid through
a circular pipe takes place, at Reynolds numbers exceeding 2100, in turbulent
flow. It could, in principle, equally well take place under laminar flow conditions,
and the latter would result in a lower pressure drop and hence a lower rate of
energy dissipation. Conversely, at Reynolds numbers less than 2100 a turbulent
flow condition would result in a lower pressure drop than laminar flow, and yet
the latter is the one which is actually encountered. Thus it is concluded that in
fact the system always chooses the flow regime where the rate of energy dissipation
is highest, rather than the flow regime where it is smallest.
This difficuty could be overcome by restricting the formulation of the prin-
ciple to situations where not only the boundary conditions are steady state, but
the actual distribution of variables is also steady state. This of course excludes
from consideration turbulent flow. One is thus left, for the case of flow of
Newtonian fluids, with only steady-state velocity distributions, and yet counter-
examples could still be easily constructed for high Reynolds number flows. One
now could restrict the scope of the principle even more, and require it to apply
only in the zero Reynolds number limit, i.e., for creeping flow.
The classical variational principle for creeping flow of Newtonian fluids,
known as the Helmholtz-Korteweg theorem, indeed produces the result that a
steady-state creeping flow solution is one which minimizes the volume integral
of a quantity proportional to the local rate of energy dissipation, and hence for
this example, and in this restricted form, the principle does indeed hold. However,
the Helmholtz-Korteweg theorem is a purely mechanical result, which is obtained
with no appeal to any thermodynamic principle whatsoever. The proportionality
of the quantity to be minimized with the rate of energy dissipation is related to
a simple dimensional argument, and is thus fortuitous. Indeed, a modified form
of the Helmholtz-Korteweg theorem can be constructed for non-Newtonian fluids
and-except in the dimensionally degenerate case of a power-law constitutive
equation-the quantity to be minimized is not proportional to the rate of energy
dissipation.
196 The point discussed in the previous paragraph is best illustrated by consider-
Chapter Seven
ing a simple one-dimensional problem: flow of a fluid between two parallel plates,
which both move with constant velocity and parallel to each other in the x
direction. If v is the velocity in the fluid (parallel to the plate velocity) and r the
tangential stress, then the momentum balance is
<I> av/at + ar/ax = 0 (7.8.2)
Since this equation implies that av/at and ar/ax have opposite signs, one has
0;0: (av/at)(ar/ax) = a(rav/at)/ax - ra(av/at)/ax (7.8.3)
If this is integrated over the distance between the two plates, the first term
vanishes, since av/at is zero on both plates. Hence
Now let us assume the fluid is Newtonian, i.e., r = -11- av/ax, where 11- is
the viscosity. We define the quantity n as
(7.8.5)
so that
r[a(av/at)/ax] = -an/at (7.8.6)
(7.8.7)
and a variational principle has been established: the solution is that which
minimizes the integral of n. This of course means that the velocity gradient is
constant, which is known to be the correct solution. The He1mholtz-Korteweg
theorem is nothing else but the generalization of this result to the general
three-dimensional formulation. Since the rate of energy dissipation is proportional
to (av/ax)2, the minimum entropy production principle happens to hold true for
this case. However, if r is a nonlinear function of av/ax, a variational principle
of the Helmholtz-Korteweg type can still be established, but the quantity to be
minimized is not proportional to the rate of entropy production unless r is
proportional to a power of av/ax.
However, let us consider the analogous heat transfer problem, with q the
heat flux. The equivalent of equation (7.8.4) now becomes
f q[a(au/at)/ax] dx (7.8.8)
(7.8.10)
q = Ldf3/dx (7.8.11)
and for the flat slab geometry a linear distribution of f3 would be expected. We
assume density is constant. Hence U = u(f3), with.
(7.8.12)
(7.8.13)
i.e., aq/ax and af3/at have necessarily equal signs. It follows that
(7.8.IS)
This argument requires T to span a range small enough that the proportional-
ity factor 1/ T2 may be regarded as constant. However, one can have steady heat
conduction with as small a temperature gradient as one wishes and still have T
ranging over a wide range, provided the slab is thick enough. Thus, no matter
how close to equilibrium one may be, the question of whether L or k is more
nearly independent of temperature is legitimate, and experimental evidence is
rather in favor of k being nearly independent of temperature.
198 Be that as it may, the important point is that, by writing linear constitutive
equations in some appropriate form, and within the restrictions discussed earlier,
Chapter Seven
it is sometimes possible to work things out in such a way that a Helmholtz-
Korteweg type of variational principle can be obtained which requires the rate
of entropy production to be minimized. However, the type of constitutive
equations required may be rather unusual, and there is no experimental support
to the idea that they are appropriate.
Biological systems are not "bodies," since they invariably exchange matter
with the environment. Any thermodynamic analysis of biological systems must
therefore be based on the formulation of the first and second law for open systems.
Let us consider in particular the very simple open system shown in Figure 7.9.1,
which has only one entering stream and only one exiting stream. (Real biological
systems are much more complex; however, the single entering stream may be
regarded as the sum of all entering streams, and the same applies to the exiting
stream.) The second law, in the form of equation (1.7.2), can be applied to a
differential mass entering the system at some time to and exiting at time to + t p ,
where t p is the residence time within the system. This requires integration of all
terms over the residence time. However, before performing the integration, it is
useful to recast equation (1.7.2) into the following form:
OP EN
SYSTEM
We first consider the case where the system may be regarded as being at
steady state. For this case, equation (7.9.3) implies that the total convective flow
of free enthalpy out of the system must be no more than the total convective
flow of free enthalpy into the system. This condition is always satisfied trivially
for biological systems, since the entering streams are typically high free. enthalpy
nutrients, while the exiting streams are low free enthalpy metabolic products.
Indeed, for a variety of fermentation processes the thermodynamic efficiency has
been measured; this is essentially the ratio of the total outflow and inflow of free
enthalpy. For those biological systems for which data are available, the thermo-
dynamic efficiency is generally of the order of 60%, and is often less than that.
The steady-state approximation is, however, open to considerable question,
for a number of reasons. Cyclic processes are known to take place in all living
systems; the same systems respond dynamically to variation in the external stimuli;
and finally, evolution is of course a crucial feature of biological systems. These
three types of phenomena, however, take place over very different time scales,
so that a hierarchy of phenomena can be considered in the temporal organization
of biological systems if the relaxation times of different phenomena can be
determined. In such a hierarchy, biophysics is at the bottom and population
genetics at the top.
The analysis of open metabolic systems is usually carried out by regarding
the concentrations of macromolecular compounds as constant (or at most slowly
changing in time) environmental parameters. This implies that the time scales
involved need to be Significantly less that those of macromolecular synthesis. The
processes considered are diffusion, interaction, and transformation by enzyme
catalysts of low molecular weight molecules, and the relevant time scale is of the
order of 10- 1_10+ 1 s. This is indeed much shorter than the relevant time scale for
the next higher system (the epigenetic one). However, a difficulty arises owing
to the very real possibility of chemical oscillations in the metabolic system. Even
if these oscillations have intrinsic time scales of the stated order of magnitude,
they are nonlinear and hence can exhibit subharmonic phenomena, which can
then interfere with the time scales involved in the epigenetic system.
Oscillations are in fact of crucial importance in biological systems, and their
analysis can be carried out on the basis of a microscopic theory which has strong
analogies with the classical statistical theory of thermodynamics. Only a brief
sketch of such a theory is given in the following. In regard to this theory, the
following points which distinguish it from the classical thermodynamic theory,
and which should always be kept in mind, are to be noted:
1. The "elementary particles" of the theory are individual cells, rather than
molecules as in the classical case. Thus the scale of description at the
microscopic level is significantly larger than in the classical case, and
statistical considerations are more loosely justified.
200 2. The miscoscopic theory is developed (and its development is still today
in a rather elementary stage) before a macroscopic formulation is avail-
Chapter Seven
able. This is in reverse order with respect to the development of classical
thermodynamics.
3. The concept of equilibrium is substituted by the concept of steady state-
and, as will be seen, in fact there is no tendency to evolve toward such
a state.
Consider the very simple feedback control loop in Figure 7.9.2, where Lis
a genetic locus which synthesizes messenger RNA at concentration, say, E. The
mRNA signals a ribosome R where an enzymatic protein is synthesized at
concentration Y. The protein influences the metabolic state at C resulting in a
metabolite M, a fraction of which loops back to L and represses the protein
synthesis. An extremely simplified model of the kinetics involved results in the
following equations for the rates of change of E and Y:
dY/dt = aE - (3 (7.9A)
E •• = (3/a (7.9.6)
However, the steady-state solution can never be reached from any initial
condition other than the steady state itself. In fact, equations (7.9.4) and (7.9.5)
can be easily combined into a single equation:
mRNA,E
and
dYldt = aGlaE (7.9.11)
which shows that they are in fact in the Hamiltonian form. A variational principle
analogous to Hamilton's principle in mechanics can be established, the variational
quantity being
Problems
7.1. Consider a solid for which the heat flux is given by equation (7.5.3). A semi-infinite body
of that solid, located at z > 0, is initially at equilibrium at a temperature To. At time zero, the plane
at z = 0 is suddenly brought to temperature T[ and thereafter maintained at that temperature.
Determine the temperature in the solid as a function of distance from the external surface, z, and time.
7.2. Obtain an estimate of the partial pressures of oxygen and carbon dioxide at the top of
Mount Everest.
7.3. As one walks up a mountain, one meets at a certain altitude the so-called tree line: no
trees grow above that altitude. Give one or more possible reasons for this phenomenon.
7.4. Estimate the significant length scale for vertical composition changes in the atmosphere
of Jupiter. You may assume that the atmosphere is made up essentially of methane and ammonia.
7.5. Describe in detail how you would set up an experiment aimed at establishing whether the
heat conductivity tensor is or is not symmetric.
7.6. Consider a system where three reactions may take place, and assume that the kinetics are
linear in the affinities. Determine the conditions imposed on the kinetic constant matrix by the second
law.
7.7. Develop a variational principle for steady one-dimensional diffusion of a dilute solute
through a solvent. Suppose that Fick's law holds with a constant diffusivity. Is the variational principle
one which minimizes entropy production? How would the constitutive equation for the flux need to
be written in order to obtain a variational principle which requires the rate of entropy production
to be minimized?
LITERATURE
In this chapter, most of the dissipative phenomena which have been considered belong
to the class usually identified with transport phenomena, the driving force being the
gradient of some potential such as temperature. The classical textbook for these is R. B.
Bird, W. E. Stewart, and E. N. Lightfoot, Transport Phenomena, Wiley, New York (1960).
However, it should be borne in mind that all phenomena of evolution of internal state 203
variables (such as, typically, chemical reactions) are also dissipative, although no gradients
of any quantity are required for such processes. The TIP literature does not clearly Dissipative
distinguish between these two types of dissipative phenomena. Phenomena
Data showing that in multi component mixtures the mobility matrix is not invariably
symmetrical are presented by P. J. Dunlap and L. J. Gosting, 1. Am. Chern. Soc. 77,5238
(1955).
The possibility that a relaxation time may appear in the constitutive equation for the
heat flux, and the consequences thereof, have been discussed by R. Ocone and G. Astarita,
AIChE 1. 33, 423 (1987); the idea goes back to the work of C. Cattaneo, Atti Sem. Mat.
Fis. Univ. Modena 3, 83 (1948). Relaxation in heat flux in Maxwellian gases was first
analyzed by J. C. Maxwell himself, Scientific Papers, Cambridge University Press (1890).
See in this regard also E. Ikenberry and C. Truesdell, 1. Ratl. Mech. Anal. 5, 1 (1956) and
C. Truesdell, J. RatL Mech. AnaL 5, 55 (1956).
The possibility that, on sudden reversal of the direction of shearing, a Maxwellian
gas may exhibit for a short time a tangential stress pointing in a direction opposite to that
of shearing is discussed by C. Truesdell, Rational Thermodynamics, Springer-Verlag, Berlin
(1984).
The fact that, if the kinetic energies of diffusion are not neglected, the diffusion
equations become hyperbolic and hence discontinuities propagate at finite speeds is
discussed by I. Muller and P. Villaggio, Meccanica 11, 191 (1976).
The literature on TIP is very abundant; it is generally difficult to read and overwhelm-
ingly confusing. The best presentation is given by K. Denbigh, The Thermodynamics of
the Steady State, Methuen, London (1951). This is also the only presentation to clarify
that, if at all, the theory is applicable only to steady-state phenomena.
The earliest, and possibly still today the clearest discussion of coupling is the analysis
of the thermoelectric effect presented by Lord Kelvin, Mathematical and Physical Papers,
Cambridge University Press, London (1922), Vol. 1, p. 232.
The viewpoint expressed in this chapter follows that of C. A. Truesdell, Rational
Thermodynamics, 2nd Ed., Springer-Verlag, New York (1985).
For a discussion of the difficulties related to the Onsager reciprocal relationships, see
B. D. Coleman and C. A. Truesdell, 1. Chem. Phys. 33, 28 (1960); and G. Astarita and
G. C. Sarti, Chim. Ind. (Milan) 57, 680, 749 (1975). The paper by J. Wei, I.E.C., Int. Ed.
58, 55 (1966) is also of interest.
While the symmetry relations are usually regarded as following from the so-called
principle of microscopic reversibility, some authors regard them as a postulate of the
theory; see, e.g., E. A. Desloge, Thermal Physics, Holt, Rinehart, and Wilson, New York
(1968). From this viewpoint, the question of proof does not arise; however, the question
of the validity of the postulate becomes crucial.
The question of the relationship between the Helmholtz-Korteweg variational prin-
ciple and entropy production is discussed by G. Astarita, 1. Non-Newtonian Fluid Meeh.
1, 343 (1977) and 13, 223 (1983).
The talandic theory of the thermodynamics of biological systems is discussed in detail
by B. C. Goodwin, Temporal Organization in Cells, Academic Press, New York (1963).
Part Two
ENGINEERING THEORY
Chapter Eight
EQUATIONS OF STATE
NOTATION
Subscripts
o At reference state
00 At infinite dilution
C At critical point
G For gas 209
~j For component i,j Equations of
k Index in series expansion State
L For liquid
S For solvent
Superscripts
0 At standard state
* For mass-based formalism
EX In excess of ideal mixture value
ID For ideal gas
1M For ideal mixture
MIX In excess of additive part
S At saturation
T Transpose
8.1. THE IDEAL GAS
U = u(T) (8.1.2)
-pV·=A·=U·-TS· (8.1.3)
and
8 = s(V, T) (8.1.5)
(8.l.8)
It follows that the constitutive equation for entropy is of the following form:
(8.1.9)
When this is substituted into equation (8.1.4) and the partial derivative taken 213
with respect to volume, one obtains Equations of
State
(8.1.10)
and thus the conclusion is reached that in a system with entropic elasticity pressure
is proportional to absolute temperature. Therefore, equations (8.1.1) and (8.1.2)
are not entirely independent of each other: if equation (8.1.2) holds, p is
necessarily linear in T.
Ordinary elastic solids are not systems with entropic elasticity. However, the
elasticity of rubbers is, to a very good approximation, entropic, and the stresses
exhibited by rubbers at any given level of deformation are proportional to
temperature. This means that rubbers appear to be stiffer at higher temperatures,
contrary to ordinary elastic solids for which the elastic moduli are generally
decreasing functions of temperature.
When work is done adiabatically on a system with entropic elasticity, internal
energy does increase, since the first law requires that. The only way for U to
increase is for T to increase, and hence the system will heat up. This does not,
however, imply that dissipation of energy is taking place, since the phenomenon
of heating upon work being done on the system may well correspond reversibly
to a phenomenon of cooling of the system when it does work, and of course that
is the case for ideal gases.
While the phenomenon of a gas with behavior not very different from an
ideal gas heating up on adiabatic compression and cooling down on adiabatic
expansion is well known, the analogous phenomenon for rubbers is somewhat
more surprising. It is easy to convince oneself of the phenomenon by stretching
a rubber band rapidly and then touching it with the lips (which are sensitive to
small temperature variations). The rubber band will be seen to be distinctly hotter
than before stretching. If the rubber band is kept stretched for a sufficiently long
time, so that by heat transfer it reaches the temperature of the surrounding air,
and is then rapidly unstretched, it will cool down well below the ambient
temperature.
Entropic elasticity is observed in materials which, on a molecular scale, are
capable of significant variations of conformational entropy. Rarefied gases are
in this category because molecule-molecule interactions are negligible, and
changes of density simply result in changes of conformational entropy. Rubbers
(and, more generally, polymers in the molten or amorphous states) accommodate
deformations by changes of the conformational entropy of the macromolecular
segments, which are long and thin enough to allow coiling and uncoiling without
significant variations of internal energy.
We now tum our attention back to the ideal gas. Mter substitution of equation
(8.1.1), equation (8.1.10) can be integrated to give
S1 = So+Rln V (8.1.11)
where So is a (so far) unspecified constant. The function u(T) is left arbitrary
in the definition of an ideal gas. For any given system, the specific heat at con~
stant volume, i.e., the derivative of the u(T) function, can be determined
214 experimentally. Thus the internal energy is given by
Chapter Eight
U = u(T) = IT cvdT+ Uo
To
(8.1.12)
and its value is thus determined to within an arbitrary additive constant. Integra-
tion of equation (8.1.7) yields, after substitution of equations (8.1.9) and (8.1.11),
S = So + IT (C
To
v/ T) dT + R In V = si T) + R In V (8.1.13)
(8.1.21)
It is important to note that the definition of ideal gas chosen in this section 215
(which is the usual one) allows the function u(T) to be arbitrary, subject to the
Equations of
requirement that it should be monotonously increasing. The Maxwellian gas is State
a special case of an ideal gas: in fact, u(T) is, for the Maxwellian gas, a linear
function of temperature, and the specific heat at constant volume is 3R/2 at all
temperatures. From this viewpoint, the Maxwellian gas is more specific than the
ideal gas as defined in this section. However, while for a Maxwellian gas equation
(8.1.1) holds at all conditions, the stress tensor is not required to be isotropic
except at equilibrium. A Maxwellian gas can sustain tangential stresses under
non equilibrium conditions, and in fact it behaves mechanically in a way which
is significantly more complex than that of a Newtonian fluid as described by
equation (2.3.A.1); see, e.g., the discussion at the end of Section 5.1. The Maxwel-
lian gas model also predicts other nonequilibrium properties in addition to
tangential stresses, such as the heat flux and the diffusive fluxes; indeed, all
molecular models can predict both equilibrium and nonequilibrium properties,
although they are most commonly used only to predict the former ones.
and
Va = I3V/I3T (8.2.2)
and
8U/ 8p = V,8(p - Tap/aT) (8.2.6)
and
8H/8p = V(l- ,8Top/aT) (8.2.8)
We now first consider a gaseous system. The difference between the equili-
brium value of any thermodynamic quantity L and the value the same quantity
would have if the system were an ideal gas, LID, can be calculated in two different
ways:
(8.2.11)
(8.2.U)
and RT In v is thus identified with the integral in equation (8.2.13). For an ideal
gas, the fugacity is equal to the pressure, and the fugacity coefficient is unity.
The above equations can be used as long as the system is a gas, i.e., up to
the pressure (or down to the volume) at which the first equilibrium phase transition
occurs. If DH and DV are known, the thermodynamic quantities in the nongas-
eous phase at eqUilibrium can be calculated from equations (4.1.8}-(4.1.11). For
example, at temperatures above the triple-point temperature, the properties of
the saturated liquid can be calculated. Equations (8.2.3}-(8.2.9) can then be used
to calculate the values of the equilibrium properties in the liquid at any other
volume smaller than the saturation volume, down to the volume at which freezing
occurs. The procedure can be repeated at every subsequent phase transition.
The compressibility of phases other than gaseous is invariably very small,
and often the approximation {3 = 0 is quite reasonable for solids and liquids.
However, a caveat is useful here. No real system is really incompressible, and
there are phenomena like the propagation of sound which are governed solely
by the compressibility. The velocity of sound is in fact equal to the inverse of
the square root of the isoentropic compressibility:
(8.1.15)
where cI> is the mass density. For an ideal gas, the right-hand side of equation
(8.2.14) is (cp / cv)(RT/ M). For liquids, the molar volume is in fact much smaller
than for gases, but the compressibility is so much smaller that sound actually
propagates in liquids faster than it does in gases. Of course, if one sets the
compressibility of a liquid to zero, one would calculate an infinite velocity of
sound. Propagation of sound is not the only phenomenon for which one cannot
regard the compressibility of a liquid as zero; the classical water hammer problem
of hydraulic engineering is another example of a phenomenon dominated by the
small, but finite compressibility of liquids.
The specific heats are given by
and
Cv = aU/aT = TaS/aT (8.2.17)
(8.2.19)
(8.2.20)
At any pressure higher than pS, the chemical potential can be calculated by 219
integrating equation (8.2.9). If the liquid is regarded as incompressible, this leads
Equations of
to State
(8.2.21)
Appendix
The third law of thermodynamics was proposed by N ernst; his argument is,
except for differences in formalism, as follows.
Given a system for which the free energy is a potential for entropy, the
following equation holds:
A=U+TaAjaT (8.2.A.l)
where, for simplicity, one may regard the partial derivative as being at constant
volume (i.e., attention is restricted to systems for which the state is V, T; however,
the argument could be generalized). Now suppose that, in the neighborhood of
absolute zero, the internal energy at constant volume can be Taylor-series
expanded:
(8.2.A.2)
(8.2.A.3)
U = Uo + O(T2) (8.2.A,5)
and
(8.2.A.6)
220 while ao is thus seen to be the entropy at absolute zero. At this point, based on
a series of considerations deriving from molecular arguments, Nemst makes the
Chapter Eight
additional hypothesis that A and U should be equal to each other as temperature
approaches absolute zero, and this of course implies that a o = O.
As discussed before, experimental verification of the third law can only be
accomplished unequivocally for some chemical reactions, for which the con-
clusion is that the standard entropy change at absolute zero is in fact zero. This
guarantees that the entropy per atom at absolute zero is the same for all those
components which participate in chemical reactions for which the check has been
made; it does not guarantee that the common value at absolute zero is zero.
It is interesting to observe that the molecular arguments used in support of
the third law are based on consideration of perfect crystals; yet Nemst thought
that only for liquids which vitrify rather than crystallize could the third law be
validated experimentally. ("Liquids, when strongly supercooled, are as a rule
frozen, and so the examination of them down to very low temperatures is rendered
impossible. We know, however, a large number of exceptions, in particular the
glasses; quartz glass may be mentioned as a striking example. Molten quartz, if
cooled sufficiently rapidly, does not crystallize, but passes continuously into the
condition of amorphous, solid quartz; the specific heat of this can be measured
without any special difficulty down to temperatures as low as may be desired.")
Note that the words "if cooled sufficiently rapidly" imply that in fact the glassy
state is not a true equilibrium state. In this regard, see also the discussion in
Section 4.5.
Another point worth some discussion is the question of the velocity of sound,
i.e., the velocity of propagation of a pressure discontinuity. Let us consider a
one-dimensional problem where the only component of velocity, U, is in the x
direction, and everything is uniform along the y and z directions. The momentum
balance, in the absence of gravity and viscosity, becomes
(8ol.A.7)
For a small perturbation about a state of rest, u = u' and iP = iPo + iP', one
may neglect all terms which are quadratic in the disturbance (primed) quantities,
and it is thus easy to eliminate u' by cross differentiation to obtain
(8.l.A.tO)
where the subscript 0 reflects the fact that the derivative is evaluated at the rest
state, i.e., at equilibrium. Equation (8.2.A.I0) is hyperbolic and admits discon-
tinuous solutions, with discontinuities propagating at a velocity (a p / aff) ) 1/2. Hence 221
the velocity of sound has been established-to within having established what
Equations of
the p(ff)) relationship may be. The usually accepted rationale for choosing the State
isoentropic compressibility is as follows: at the surface of discontinuity, there is
no heat flux, hence it is adiabatic, and if reversible the process is isoentropic.
There are important conceptual difficulties with this argument (suffice it to
consider that, at the traveling discontinuity, since pressure undergoes a discon-
tinuity, so does temperature, and hence the temperature gradient is infinitely
large), but it does lead to the correct result as far as the velocity of sound is
concerned. Whether the same argument can be duplicated for other types of
shock propagations is open to question.
For the writer ojJantastic stories to help the reader to play the
game properly, he must help him in every possible unobtrusive
way to domesticate the impossible hypothesis. He must trick
him into an unwary concession to some plausible assumption
and get on with his story while the illusion holds.
H. G. Wells
Section 8.1 was dedicated to the ideal gas involving a constitutive equation
for one-component systems that has two important properties: first, it is extremely
simple, and second, it is appropriate for the description of real one-component
systems at least under some limiting but realistic conditions. Section 8.2 dealt
with the introduction of correction coefficients for real systems which do not
necessarily behave as ideal gases. One may now follow a similar approach for
the case of mixtures. First, in this section we introduce the definition of a special
class of mixtures, which are called "ideal." The constitutive equation for ideal
mixtures is both very simple and is adequate for real systems at least under some
limiting but realistic conditions. In the next section we define corrections
coefficients for mixtures which deviate from the behavior of ideal mixtures.
As was discussed in Chapters 3 and 4, equilibrium calculations for both
chemical reactions and phase equilibria require knowledge of constitutive
equations for the chemical potentials as a function of composition, i.e., as a
function of the mole fraction vector y. Consideration of quantities which are
functions of composition presents some subtlety. Of course, one can write a'n
equation of the following form for the density L of any extensive quantity which
depends on composition:
(8.3.1)
with the partial derivatives being of course baric derivatives. However, partial
derivatives with respect to the mole fractions have no meaning, since if one of
the mole fractions changes, the others cannot all remain constant.
222 Let us now consider the total quantity L" which can be written as
Chapter Eight
(8.3.2)
If nj is changed by an amount dnj and all the others are kept constant, the
corresponding dL, is
(8.304)
(8.3.5)
.~
A
..
··
L
·... K
P L = 8L'/8y (8.3.7)
p[. y = 0 (8.3.8)
(8.3.9)
(8.3.10)
with f(Yi) an as yet unspecified function. The Gibbs-Duhem equation can now
be used to express 8ILd 8Yi in terms of f(y;):
(8.3.11)
This equation shows that one cannot simply assign f(Yi) = O. Now the value of
f(y;) has dimensions of an energy density and can depend at most on temperature
(see the discussion in Section 8.8). Thus the simplest possible form for f(y;) is
(8.3.12)
and correspondingly
(8.3.13)
Solutions described by equations (8.3.12) and (8.3.13) are called ideal. The
strength of this definition of ideal solutions is not only its simplicity, but the fact
224 that gaseous mixtures at moderate pressures and some liquid solutions are in
fact adequately described by it.
Chapter Eight
Equation (8.3.13) can be integrated directly between any two mole fractions
Yjl and Yj2 to yield
(8.3.14)
(8.3.1S)
(8.3.17)
(8.3.18)
V'=VO (8.3.19)
Le., the partial molar volumes are constant and equal to the pure components'
volumes. This in turn implies that the volume of an ideal solution is additive, Le.,
(8.3.20)
which implies that entropy is not additive. For nonadditive extensive properties,
the mixing value is defined as follows:
L MIX = L - Y• L° (8.3.22)
(8.3.25)
and that must be equal to the equilibrium partial pressure of water vapor in the
saturated air, py, which can be measured. Thus it is concluded that the constant
f O appearing in equation (8.3.18) is
(8.3.26)
This point will be discussed in more detail in the section on dilute solutions.
In contrast to gases, liquid mixtures are generally not ideal solutions, unless
all components have closely analogous molecular structures.
226 8.4. ACfIVITY COEFFICIENTS
Chapter Eight
In the course of its development, a physical theory is free to
choose whatever way it pleases, provided logical contradictions
be avoided; in particular, it is free to take no account of
experimental facts.
It is not the same when the theory gains its full development.
When the logical structure has reached its full height, then we
must compare the whole of its mathematical propositions,
obtained as conclusions from these long deductions, with the
whole of the facts of experience.
P.Duhem
(8.4.1)
(8.4.2)
where LIM is the value of L one would calculate from ideal mixtures theory. For
those properties which are additive in ideal mixtures, LEX coincides with L MIX.
The excess properties can all be expressed in terms of the activity coefficients:
UEX = U MIX = RTy • (In'T - Tl3 In 'T/ l3T - pl3 In 'T/ l3p) (8.4.8)
Equation (8.4.3) implies that the Gibbs-Duhem equation holds for the In'T
vector, say
limln'Tj=O (8.4.11)
'Tj=l
The Gibbs-Duhem equation for componentj implies that 227
Equations of
lim(S In 'T) SyJ = 0 (8.4.12) State
Tj=l
(8.4.14)
and therefore G EX approaches zero linearly when any of the mole fractions
approaches unity.
Equation (8.5.1) implies equation (8.4.12) provided the baric derivative appearing
on the right-hand side does not approach infinity when y approaches unity, at
least not as rapidly as 1/(1 - y). The theory of dilute solutions is based on the
assumption that indeed such baric derivatives always satisfy the stated restrictions.
It should be noted that the conclusion that the solvent's activity coefficient is
unity is a first-order approximation, since deviations are of the order of (1 _ y)2.
This, as will be seen in Section 8.8, is a very important result. In fact, while
dilute solution theory is a zero-order approximation as far as the solutes are
concerned, it happens to be a first-order approximation for the solvent, and
228 within the first order the solvent behaves as if the solution were ideal. This makes
possible experimental verification of the theory.
Chapter Eight
The activity coefficient of the solute can be expressed as
(8.5.2)
and hence, to within the zero-order approximation, it can be taken constant and
equal to its value at infinite dilution, 'Tleo'
Now we suppose that another solute is added to the system, but in small
enough an amount to maintain the solution dilute, so that Y2 is of order 1 - y.
The activity coefficient for the first solute can be written as
(8.5.3)
and therefore, again to within the zero-order approximation, it can be taken equal
to its infinite dilution value. The procedure can obviously be reiterated, and one
concludes that all the activity coefficients can be regarded as constant:
T = Teo (8.5.4)
(8.5.5)
(8.5.7)
Consider the case of a binary mixture, and let the fugacity of one of the
components vary with its mole fraction as in Figure 8.5.1. Raoult's law corresponds
to the lower straight line, and Henry's law to the upper one, which by definition
is tangent to the curve at the origin. The Raoult's law line is tangent to the curve
at y = 1 because of equation (8.4.12).
limpVIRT=1 (8.6.1)
t/v"'o
pVIRT=I+IadVk (8.6.2)
which can be employed with the sum truncated after some finite number of terms
as the equation of state for a one-component system. Equation (8.6.2) is called
the virial equation of state, where ak are the virial coefficients. The latter can be
obtained either by fitting experimental data, or from an appropriate molecular
model. The series expansion in equation (8.6.2) is in terms of II V. and hence is
at some fixed T; consequently, the coefficients ak could well depend on T.
Of course, the power-series expansion cannot be valid over a phase transition,
where the molar density suffers a discontinuity. Therefore, in order to use the
virial equation of state for nongaseous systems, one has to assume that it represents
the one-phase behavior through the phase transition, say a continuous curve such
as in Figure 2.6.1. This in turn implies that the derivative apjaV must change
sign twice when going through any phase transition.
The derivative is
(8.6.3)
and therefore every additional change of sign requires two more terms in the
series. If the equation must be used through several phase transitions, the number
of terms needed becomes large enough for calculations to be cumbersome. If the
equation is used only for the liquid phase (or the solid phase in the case of
sublimation at temperatures low enough for the intermediate bump in Figure
4.4.1 to have disappeared), two nonzero virial coefficients are the minimum
requirement, since a third-order polynomial may have the shape in Figure 2.6.1.
The virial equation of state has as many parameters as there are terms in the sum
retained.
The Van der Waals constitutive equation is a slight modification of the
two-parameter vi rial equation of state, since the first term in the series is written
as all (V - at). This of course implies that a l is the smallest possible volume of
the system, since pressure approaches infinity when the volume approaches a l •
For the classical virial equation of state, pressure approaches infinity only when
the volume approaches zero.
It is of interest to consider the dimensionality of the equation of state. Since
p, Vand T are dimensional quantities, the mathematical form ofthe f( . ) function
depends on the choice of the units of measurement. It can always be made
dimensionless (Le., invariant with respect to a change of units) by introducing
three dimensional parameters having units of pressure, volume, and temperature:
v= VeT) (8.6.5)
Appendix
The Van der Waals equation of state can be expressed in the form
and is thus a cubic with two adjustable parameters (a and b). The values of the
two parameters can be chosen in such a way as to satisfy the conditions required
at the critical point:
Hence
b = Ve /3 (8.6.A.3)
and
a = 9RTe Ve /8 (8.6.A.4)
Now, of course, whether one third of the critical volume is really the lowest
possible attainable volume is open to question. However, this is not the important
point, since the Van der Waals equation is not supposed to be valid at extremely
high pressures. It is of more interest to consider variations of the Van der
Waals equation which have been used with varying degrees of success. The
most commonly used variation is the Redlich-Kwong equation, which can be
232 written as
Chapter Eight
p = RT/(V - b) - a/[JT(V2 + bY)] (8.6.A.5)
and again has only two (constant) parameters, but is more successful than the
original Van der Waals equation in fitting data. Addititional refinements have
been considered in the literature. Values of the parameters and functions appear-
ing in such equations have generally been constrained by the requirement that
equation (8.6.A.2) should hold at the critical point.
(8.7.1)
with a being the only parameter. From equation (8.4.14) one obtains
(8.7.2)
and
In T2 = ayi (8.7.3)
Equations (8.7.2) and (8.7.3) are the "one-suffix" Margules equations for the
activity coefficients. A few binary mixtures are adequately described by them.
Let us return to the discussion in Section 4.2. In order to have a two-phase
equilibrium system, the curve of gEX vs. Yt must have a spinodal region, i.e., its
second derivative or curvature, C, must be negative for some values of Yt. For
an ideal solution 233
Equations of
(8.7.4) State
which is intrinsically positive-and in fact infinity when either of the two mole
fractions approaches zero. Since a EX approaches zero linearly in both limits, e
is necessarily positive in those limits-implying that complete immiscibility can
never occur. For a binary mixture adequately described by equation (8.7.1), the
value of e is given by
e = e lM -2a (8.7.5)
and thus a spinodal region will occur provided a> 2 (the minimum value of
elM is 4). Of course, the value of a may be either positive or negative. Mixtures
for which gEX is positive are said to exhibit positive deviations from ideality,
and in actual fact represent the most common case. Mixtures which exhibit
negative deviations from ideality generally do not exhibit a miscibility gap, though
mathematically it would not be impossible to write a constitutive equation for
gEX such that gEX < 0 but e < 0 for some YI'
which yields
and
In'T2 = yi(b20 - b1Y2) (8.7.8)
where
blO = ao + a2 (8.7.9)
b20 = ao + al (8.7.10)
which results in
(8.7.13)
and an analogous equation for In 72' Equation (8.7.12) is the Van Laar equation
for activity coefficients; higher-order Van Laar expansions, as well as higher-order
Margules equations, are of course possible.
Higher-order Margules-type approximations simply lead to the following
type of constitutive equation for the activity coefficient of component 1:
(8.7.14)
(8.7.15)
with 1(0) = 0 in order to be consistent with the theory of dilute solutions. The
value of blO is of course the value of In 7100'
Let us now consider ternary mixtures, for which the simplest form of
constitutive equation for gEX is
(8.7.16)
(8.7.17)
and the equations for the other activity coefficients are obtained by cyclic permuta-
tion of indices.
Although Equation (8.7.16) is legitimate, it contains a conceptual problem.
While the properties of ideal mixtures can be calculated by knowing only proper-
ties of the pure components, that is not true for nonideal mixtures: in the binary
case, even the simplest possible constitutive equation (the Margules equation)
contains a parameter which can only be measured by experiments conducted
with the mixture itself. Now for equation (8.7.16), consider the situation where
Y3 is zero. The last two terms drop out, and thus the value of al2 could be
determined by experiments conducted on the binary mixture of components 1
and 2. A similar argument holds for the other two parameters, and therefore one
would conclude that the properties of the ternary mixture can be predicted by
measurements carried out only on the three binary component mixtures. That
does not appear very convincing. Indeed, it is natural to regard the au parameters 235
as interaction parameters, and thus equation (8.7.16) only accounts for binary
Equations of
interactions, while in a ternary mixture ternary interactions are possible. State
In fact, the problem discussed above disappears in the next-order approxima-
tion, which allows for ternary interactions:
This produces for the activity coefficients equations of the following form:
Clearly, the b123 coefficient can only be obtained from experiments conducted
on the ternary mixture itself.
The above argument can be reiterated as any new component is added: with
only binary and ternary interactions, the behavior of a 4-component mixture can
be predicted from the results of experiments performed only on the 4 ternary
component mixtures, and so on. In general, experiments on the N-component
mixture itself will be needed whenever N-ary interactions are allowed for. If one
allows only interactions up to, say, M-ary interactions, then experiments are
needed only for mixtures up to M components, and the behavior of mixtures
with more components can be predicted from these.
Since there is always some conceptual problem with the idea that the behavior
of a mixture can be predicted without any experiment being conducted on the
mixture itself, one would like to allow for N-ary interactions at least. But, as the
examples in this and the preceding section have shown, the algebraic complexity
and the number of parameters grow very rapidly as either the order of the
interactions or the number of components grow. The algebraic complexity could
be handled by modern computing facilities, but the large number of parameters
to be determined experimentally creates problems of accuracy of measurement
which cannot be circumvented. It is therefore clear that predictions obtainable
from molecular models are particularly important in this area.
Except for the discussion in Section 7.3, the thermodynamic theory developed
so far is all based on the use of molar units. It should be kept in mind, however,
236 that it could equally well be developed in mass units. The preference for molar
units is, for the material discussed so far, essentially a matter of convenience.
Chapter Eight
With molar units, the stoichiometric coefficients for chemical reactions are small
integers, which is preferable to the noninteger values which would be needed for
mass units. The ideal gas law has the universal constant R when molar units are
used, while it would have different values for different gases if mass units were
used (the mass-based constant being R/ M). Partial mass properties L" can be
defined in perfect analogy with the partial molar ones L'; ·the former are simply
the latter divided by the molecular weight of the component considered, i.e.,
L" = L'/ M. Since the Gibbs-Duhem equation is simply a consequence of the
fact that extensive properties are absolutely additive functions of mass, it holds
for partial mass properties as well.
A crucial difference, however, arises in the definition of ideal mixtures. The
mole-based definition is given in equations (8.3.9) and (8.3.10), which reduce to
equation (8.3.13). One could perform the same algebra in mass-based units and,
if w is the weight fraction, one would obtain for the mass-based chemical potential
(identified by an asterisk)
(8.8.1)
Since the Gibbs-Duhem equation holds for JL * and for In w, with this definition
it also holds for In T*.
Let us consider a solution which is mole-based ideal, say equation (8.3.13)
holds. Since JL * = JL/ M, one obtains
i.e., a mole-based ideal solution is not ideal in the mass-based formulation, and
vice versa. This is the crucial reason for choosing the mole-based formulation:
gases at moderate pressures are mole-based ideal solutions, while there is no
concrete case described by the mass-based ideal solution definition. Of course,
this conclusion is supported by molecular-type arguments: in the Maxwellian
theory of dilute gases, the "particles" are molecules, endowed with a mass
proportional to their molecular weight.
The point made in Section 8.3 about the strength of the theory of mole-based
ideal mixtures is now reinforced. A mass-based ideal solution is one where the
chemical potential of every component depends only on its own weight fraction,
and is independent of what the weight fractions of other components may be,
and of their number and nature. This is as simple as a mole-based ideal solution, 237
but is not realistic-no real system is mass-based ideal. Equations of
One could also choose an alternate approach for the mass-based formalism: State
one could omit entirely the definition of ideal solution and use equation (8.8.2)
as a definition of the mass-based activity coefficients T*. One would now obtain
the following relationship between mass-based and mole-based activity
coefficients:
and one is tempted to choose the constant A as RT/ M. Such a selection would
make the constant in equation (8.8.2) dependent on temperature and on the
nature of the component considered, but not on the nature of the other com-
ponents. However, there are two problems with such a choice. First, since now
A does depend on the nature of the component considered, the Gibbs-Duhem
equation would hold for A In( WT*) and for In w, but not for In T*. Second, and
even more important, with such a choice (or with any choice where A is not a
universal constant at any given temperature) under no conditions could T* be
unity, since if it were the Gibbs-Duhem equation would not be satisfied.
The point is particularly relevant to the behavior of the solvent in a dilute
solution, since this is assumed to be what would be observed in a mole-based
ideal solution (in the first-order approximation)-and hence it is not what would
be observed in a mass-based ideal solution. For the solvent, T = 1, and if Y is
the sum of the. mole fractions of all solutes and W the sum of their mass fractions,
in the first-order approximation equation (8.8.4) reduces to
where M is the molecular weight of the solvent. We note that even the choice
A = RT/ M does not make T* = 1, except when the average molecular weight
of the solutes, M', is equal to M. In the first-order approximation, WM = YM',
and hence the choice A = RT/ M' would indeed give T* = 1; however, this would
imply that the definition of the solvent's activity coefficient depends on the nature
of the solutes-which is of course totally unacceptable. Hence the only sensible
way of developing a mass-based formalism would be to define ideal solutions
by equation (8.8.1), with A depending only on temperature.
Of course, from a purely descriptive viewpoint the mass-based formalism is
perfectly equivalent and, based on the same sequence of assumptions, one would
obtain for the fugacity of the solvent in a dilute solution
(8.8.6)
(8.8.7)
(8.8.8)
The important point about equations (8.8.6) and (8.8.8) is that the right-hand
side depends on Y, but is independent of the nature and the relative amounts of
the solutes. This statement is not equivalent to that obtained by substituting W
for Y in it, and the theory of colligative properties discussed below can only
apply to one formulation-under the restrictions discussed above, it applies to
the molar-based formulation. The most important colligative properties are (under
appropriate qualifying conditions) the boiling temperature, the freezing tem-
perature, and the osmotic pressure. These are discussed in the following.
The boiling temperature is a colligative property if all the solutes have
negligibly small volatilities, so that when boiling occurs the vapor phase consists
of the pure solvent. Let us first examine the case when the solvent vapor can be
regarded as an ideal gas, so that at the equilibrium boiling point its fugacity is
equal to the pressure on the system. Quantity f O is, for the same case, the vapor
pressure of pure solvent. The equilibrium boiling point corresponds to the
temperature at which f becomes equal to the total pressure: since f is less than
f O, this corresponds to a higher boiling temperature than that of the pure solvent.
Without any approximation, the boiling-point increase can be calculated as
,follows. Considering equation (3.3.16), the partial molar enthalpy of the solvent
can be written as
(8.8.9)
An analogous equation can be written for the pure vapor. Since the properties 239
of the solvent are the same as would be observed in an ideal solution, H' is the Equations of
enthalpy of the pure solvent. Substitution of equation (8.8.2) and integration yields State
RY = fT (DH/T2) dT (8.8.10)
Ts
where T is the boiling point of the solution and Ts that of the pure solvent.
Equation (8.8.10) is seen to contain no properties of the solutes, and hence it
can be used to extract the value of Y from the measurement of T.
The freezing temperature is a colligative property if the solid phase which
forms upon freezing essentially consists of the pure solvent. This is in fact often
the case. Equilibrium freezing occurs when the chemical potential of the solvent
is equal to that of the pure solid. The latter decreases with temperature at constant
pressure, and hence freezing occurs at a temperature lower than it would for the
pure solvent (that is the reason why salt is sprayed on snow to melt it: the freezing
point is lowered by the addition of salt). Equation (8.8.7) is obtained again, with
the limits of integration reversed, and with DH being of course the latent heat
of fusion.
Finally, we consider the case of osmotic pressure. The pure solvent fugacity
f O increases with pressure at fixed temperature, and one can ask at what pressure
the fugacity of the solvent in the solution will equal that of the pure solvent at
pressure p; the difference is called osmotic pressure, pOs. A straightforward
calculation for the case where the liquid is incompressible yields
(8.8.lt)
Problems
8.1. Consider a dilute solution for which the gas and solid phases consist of the pure solvent,
with the solutes present only in the liquid phase. Draw a pressure-temperature phase diagram for
the case where also the liquid phase consists of the pure solvent, and for the case of the solution,
and infer graphically the boiling point increase and the freezing temperature decrease. For the same
system, draw a chemical potential vs. temperature diagram at a fixed pressure, and again infer the
two colligative properties from such a plot.
8.2. Consider the gas represented by (a) the virial equation of state, (b) the Van der Waals
equation of state, and (c) the corresponding states equation. Which, if any, are systems with entropic
elasticity? Which assumptions did you make in getting your answer, and can some of these be proved?
Does the fact that gases usually behave as ideal mixtures support your conclusion?
8.3. Consider the quantity g(T) defined in equation (8.1.17). Is the sign of the derivative dgldT
fixed, and if so, what is it? Does the result hinge on the application of the third law?
SA. Does the corresponding states equation as defined in Section 8.6 imply that the quantity
Pc Vcl RTc is a universal constant?
8.5. Write the appropriate second-order equation corresponding to the expansion in equation
(8.7.12).
8.6. Can equation (8.7.12) predict phase separation? If it can, what constraints must the
parameters A and B satisfy in order to have a spinodal region?
8.7. Calculate the mole fraction of styrene in a 1% by weight solution of styrene in polystyrene.
The polystyrene has a molecular weight of 2 million. Do you think it realistic that Henry's law, or
some modification thereof, could be used to describe the solubility of styrene vapor in polystyrene?
If you do, write down the modification that you think is realistic.
8.8. If you add salt to water before it boils, will the time needed to bring it to boiling be more
than, less than, or equal to the time needed without salt? Give an estimate of the percentage difference
if you think there is one.
8.9. Calculate the osmotic pressure of seawater. Do you think it realistic that it could actually
be measured by an equilibrium experiment, even if a truly semipermeable membrane could be found?
How would you set up the experiment?
LITERATURE 241
Equations of
Mathematics is an obscure field, an abstruse science,
complicated and exact; yet so many have attained peifection in State
it that we might conclude almost anyone who seriously applied
himself would achieve a measure of success.
Among [the Greeks] geometry was held in highest honour;
nothing was more glOriOUS than mathematics. But we have
limited the usefulness of this art to measuring and calculating.
Cicero
PHASE EQUILIBRIA
NOTATION
Subscripts
Superscripts
I, II For phase I, II
* At equilibrium
EX In excess of ideal mixture
G For gas phase
ID For ideal mixture
L For liquid phase
S At saturation
9.1. GAS-LIQUID EQUILIBRIA
where v' is the fugacity coefficient of A at a pressure equal to p', and the fugacity
correction (3 for pressure in the liquid has been given based on the assumption
of incompressibility of the liquid phase. If the pressure is low enough for the
gas mixture to be ideal (a much milder requirement than the condition that the
fugacity coefficients should be unity), one can write
/=pvy (9.1.2)
y = p'v'(3/pv (9.1.3)
If all fugacity coefficients can be taken as unity, and if the pressure correction
for the liquid phase is neglected, this reduces to the classical elementary result
(9.1.5)
If the gas phase is an ideal mixture, the gas phase fugacity is given by
equation (9.1.2), and therefore the equilibrium condition in the absence of
capillary effects can be written as
(9.1.6)
(9.1.7)
First we consider the simplest possible case where the liquid phase is an
ideal solution, so that equation (9.1.7) reduces to Raoult's law:
The boiling point of the liquid mixture at any given pressure p is determined
by the requirement that equation (9.1.8) must be satisfied for all components
with quantities yy summing to unity, and the dew point by the requirement that
it should be satisfied with all the quantitiesy;summing to unity. The dew points
and boiling points of the mixture are always intermediate between those of the
highest boiling and lowest boiling pure components. A plot of dew and boiling
points for an ideal binary mixture is presented in Figure 9.1.1. Given an average
composition of the mixture such as y, and a temperature T, such that the point
y, T lies within the lense-shaped region, the equilibrium condition will be a
two-phase one, with the liquid- and gas-phase mole fractions being determined
by the intersection of the horizontal through T with the dew and boiling point
curves, and the relative amount of the two phases being given by the usual lever
rule applied to that horizontal segment. This is true also for nonideal solutions,
where the two-phase envelope may have a shape quite different from the simple
lense in Figure 9.1.1.
Next let us consider the case of a binary nonideal mixture. It is useful to
define a relative volatility a as follows:
(9.1.9)
(9.1.11)
and it may well change from larger to smaller than unity if a liquid-phase
composition exists for which
a=l (9.1.2)
(9.1.3)
(9.1.14)
Often, the quantity in parentheses is called the Henry's law constant. The
distinction becomes irrelevant if the pressure is low enough so that v = 1.
Appendix
h = 2s/r (9.1.A.l)
where r is the radius of the embryo. The chemical potential within the embryo
is thus
(9.1.A.Z)
252 The number of moles in the embryo is ~1Tr3I VL • The total free enthalpy of
Chapter Nine
the embryo, including the surface excess free enthalpy, is thus
The same amount of condensable component in the gas phase has a total
free enthalpy ~1Tr3 I-' G I VL , and hence the driving force for growth of the embryo
is
(9.1.AA)
The embryo will tend to grow, provided the right-hand side of equation
(9.l.A.4) decreases with increasing radius. We note, however, that at small values
of r the negative second term will predominate, and therefore embryos formed
by Brownian motion will tend to redisperse again in the gas phase. The critical
embryo radius is that for which the derivative of 8Gt with respect to r is zero:
= (3 VL s/10)[RTln(plp')] (9.1.A.5)
where p is the partial pressure of the condensable component in the gas phase.
An estimate of the actual value of pip· needed for significant growth. of
embryos can be obtained by absolute rate theory, with the relevant energy being
the value of 8G, corresponding to the r value in equation (9.1.A.5). The rate of
growth thus calculated exhibits almost a sharp discontinuity at a critical value
of pip" which may be as large as 5 for growth of water embryos in cool
atmospheric air.
The above discussion is concerned with homogeneous nucleation. In actual
fact, nucleation occurs preferentially on seeds, which in the case of atmospheric
formation of fogs and clouds are microscopic salt grains. If one considers a very
small drop of water containing the original salt seed, two opposing effects take
place. On the one side, as r is increased, capillary effects have the same behavior
as discussed above. On the other side, as r grows the mole fraction of water in
the embryo increases, and thus its equilibrium vapor pressure increases. Indeed,
at very small radii the latter effect is predominant, so that the chemical potential
of water in the concentrated salt solution corresponding to the original embryo
is very low. This is the reason why nucleation on salt seeds predominates over
homogeneous nucleation.
Let us consider a binary nonideal mixture which exhibits an azeotrope at
some fixed pressure p. Gas-liquid equilibrium occurs when
(9.1.A.6)
(9.1.A.7)
which, in view of equation (9.1.12), shows that the boiling temperature of the 253
azeotrope is an extremum. The second differentiation shows that it is a maximum Phase Equilibria
for positive deviations from ideality, and vice versa. The argument is easily
generalized to more than two components.
Out of whose womb came the ice? And the hoary frost of
heaven, who hath gendered it? The waters are hid as with a
stone, and the face of the deep is frozen.
Job 38, 29-30
(9.2.1)
(9.2.3)
YA = Yo = (1 - Yd/2 (9.2.4)
The curvature of the ideal-solution free enthalpy curve along the vertical
line is
and has a minimum of 5.828 at Yc = .J2 - 1. The curvature of the excess free
enthalpy curve along the vertical line is
(9.2.6)
and thus it may well be positive or, if negative, its absolute value may well be
less than 5.828, so that no miscibility gap will occur. Indeed, the stronger the
immiscibility between A and B, the more likely it is that no miscibility gap will
be observed along the vertical line. This point is very important for realizing
miscible polymer blends, since polymers very often exhibit strong immiscibility;
however, if the least miscible pair is copolymerized, it becomes miscible with the
third polymer.
The algebra becomes rapidly very cumbersome as the number of components
is increased, and hence a continuous description of the type discussed in Section
9.5 becomes useful. For a three-component mixture, the curvature of the excess
free enthalpy surface over the Yl-Y2 plane is given (to within a multiplicative
constant) by
(9.2.7)
c c
a B A B
b
A
C
which is always positive, with a minimum value of 15 when all three mole fractions
equal ~.
(9.3.1)
(9.3.2)
in the first-order approximation (Le., with the activity coefficient of the solvent
taken to be unity). The value of TE is determined by the following condition:
(9.3.5)
In the zero-order approximation (Le., yl "" 1 and 1 - yll "" 1) this reduces
to the condition that the sum of the vapor pressures of the two components
equals the total pressure.
It is of interest to determine the conditions under which TE is lower than
the boiling temperature of both components. Since the vapor pressure is a
monotonously increasing function of temperature, it can be inverted to yield a
function (J:
and the boiling point of the two components are simply 1J.(p) and 1J2 (p). If R
is the vapor pressure ratio p~/ p~, with the labeling of components chosen so that
R> 1, and thus (J.(p) < (J2(P), then TE is obtained from equation (9.3.5) in the
form
(9.3.7)
(9.3.8)
which is, of course, more easily satisfied the larger the miscibility gap.
The essential feature of the phenomenon discussed above is the following.
When a large miscibility gap exists in the liquid phase, the fugacity of component
1 in phase I (as well as that of component 2 in phase II) increases rapidly with
temperature because so does the vapor pressure; the effect of temperature on the
activity coefficients and on the fugacity coefficients of the saturated vapor is much
weaker. In the gas phase, the fugacity of each component decreases with decreas-
ing mol fraction, and is at most a weak function of temperature. It follows that
I
lI+I1 II
I
I
FIGURE 9.3.3. Phase diagram for a system
exhibiting a miscibility gap in the liquid phase.
T
259
Tt.11
Phase Equilibria
II
(9.3.9)
x x
x x
(9.4.1)
with type III being obtained if c < 1. The BET equation contains two parameters
(x M and c), and it does predict the obvious result that, as p approaches p", x
approaches infinity (an actual liquid phase is formed). If T> Te, the BET
equation could be regarded as having three parameters, though the value of pS
is expected to be close to what one would calculate from extrapolation of the
vapor-liquid equilibrium curve beyond Te. Type IV and type V adsorption
isotherms can be correlated by modifications of the BET equation which contain
additional parameters.
Hysteresis has been explained in terms of capillary effects (hysteresis of the
contact angle, or different geometries of the menisci in adsorption and desorption)
and in terms of swelling phenomena. The latter are particularly important in the
262 case of polymers, and since swelling in polymers takes place at a rate governed
by its intrinsic kinetics, hysteresis is clearly seen to be in fact a kinetic
Chapter Nine
phenomenon.
Finally, adsorption phenomena are often separated into two classes: physical
and chemical adsorption; an actual chemical bond between sorbate and solid is
assumed to be formed in the second case. The separation is somewhat arbitrary,
but three macroscopically observable phenomena can be employed. First, the
heat of chemical adsorption is in general significantly larger, being of the order
of magnitude of the enthalpy change of a chemical reaction. Second, chemical
adsorption may proceed at rather slow rates, since it is essentially a chemical
reaction, while physical adsorption equilibria are generally achieved very quickly.
Finally, chemical adsorption is always confined to a molecular monolayer. In
some cases, chemical adsorption prevails at low partial pressures, while physical
adsorption is observed at higher values of p.
If you do not expect it, you will not find the unexpected,
for it is hard to find and difficult.
Heraclitus, On Nature, VII
a = f n(u) du (9.5.1)
where M' is the second moment of the liquid-phase mole fraction distribution
(the first moment is unity by definition). Hence one obtains
(9.5.5)
(9.5.6)
(9.5.8)
(9.5.9)
and is thus seen to be sharper than the liquid phase quantity. Even in the case
of Raoult's law, the shape of the mole fraction distribution in the vapor phase
differs from that in the liquid phase.
We next consider the case of a nonideal liquid phase in equilibrium with a
gas phase which behaves as an ideal gas, and suppose that the pressure correction
in the liquid phase is negligible. One cannot now use b as a label, since two
components with the same vapor pressure b may well have different activity
coefficients, and thus a true label u is needed. The activity coefficient of component
u, r(u), is defined by
(9.5.11)
264 and the total pressure is
f f
Chapter Nine
p = pyG(u) du = r(u)b(u)yL(U) du = M" (9.5.12)
where now, however, M" is not the second moment of the liquid-phase mole
fraction distribution. The mole fraction distribution in the gas phase is
(9.5.13)
and will of course in general have a shape different from that of the liquid-phase
distribution. However, this is not necessarily so, and in fact it is possible to have
a continuous azeotrope. Indeed, the activity coefficient distribution will in general
depend on the liquid-phase composition:
may have a solution for a particular distribution yL(U). That distribution then
corresponds to a continuous azeotrope, since the gas phase and the liquid phase
will have the same composition.
In order to actually carry out calculations for nonideal solutions, it is of
course necessary to write down constitutive equations for the activity coefficients.
These must be obtained from some appropriate generalization of equations written
for mixtures of a few components. A brief sketch of the methodology is given
below for a particularly simple case.
In an ideal solution, the free enthalpy of mixing is given by (the superscript
L is omitted for simplicity)
(9.5.17)
and write constitutive equations for it. We now consider the special case where,
for a two-component mixture, the one-parameter Margules equation is adequate,
say equation (8.7.1) holds. For an N-component mixture, if only binary interac-
tions are allowed for, one would write
(9.5.18)
where the second sum is over K different from I, alK = aKI, all = 0, imd 265
gEX = OEX/ RT. The continuous generalization is
Phase Equilibria
(9.5.23)
(9.5.24)
(9.5.25)
f a(w)dw=1 (9.5.26)
with y(u; w) being the mole fraction distribution in phase w. The convexity
condition becomes
Examples
K = Kcexp(-Q/RT) (9.E.l)
One may now ask the following question: if one had a choice of sorbant solids, what
value of Q would one want to have in terms of minimizing the energy requirements of
the process?
It would seem at first sight that one requires as low a value of Q as possible, since
one certainly has to provide the heat of desorption in the regeneration step. However,
things are more subtle than that. Let x be the value reached in the adsorption step, and
choose a unit mass of sorbate-free solid as the basis for calculation. The temperature
swing DT required (i.e., the temperature difference between the adsorption and regener-
ation steps) is determined by the partial pressure ratio between extract and reject, which
is a specification of the problem. Linearization of equation (9.E.1) in the temperature
difference DT yields the result that DT is in fact inversely proportional to Q:
There are in fact two heat requirements: the amount needed to heat a mass 1 + x
over a temperature swing DT, which is roughly proportional to (1 + x)DT, and the heat
of desorption, which is proportional to xQ, so that the total energy requirement E is
Problems
9.1. Draw a dew point-boiling point plot for a system exhibiting a miscibility gap in the liquid
phase but no three-phase azeotrope.
9.2. Consider a binary mixture for which the activity coefficients are given by equations (8.7.2)
and (8.7.3). Suppose that the ratio R = p~/ p~ is constant with temperature. Establish conditions for
the values of a and R which will result in the existence of a three-phase azeotrope.
9.3. Consider the plot in Figure 9.3.1. Is component 1 necessarily the one with a larger vapor
pressure, as Figure 9.3.3 implies?
9.4. You have certainly observed that when you add some watery food such as tomatoes in
a pan where some oil has been heated up, violent boiling results, which however ends very rapidly.
When the boiling is observed, is the temperature of the oil necessarily more than 100·C? Why do 267
you think the boiling ends rapidly to be substituted by gentle simmering?
9.S. There is no general consensus in the literature on the definition of the r function. Let the Phase Equilibria
argument 0 be an integer; then the two definitions found are such that nO) is either the factorial
of 0 or the factorial of 0 - 1. Which is the definition which applies to equation (9.5.9)?
9.6. Prove that, when 0 approaches 00 in equation (9.5.6), one correctly recovers the one-
component result p = Q.
LITERATURE
There is such an ample literature on phase equilibria that it is difficult to provide any
reasoned guide. Three classical books are M. B. King, Phase Equilibrium in MixlUres,
Pergamon Press, Oxford (1969), A. Reisman, Phase Equilibria, Academic Press, New York
(1970), and J. E. Ricci, The Phase Rule and Heterogeneous Equilibrium, Van Nostrand,
New York (1955).
Of the books more specifically dedicated to special topics, the following are useful
references: A. W. Francis, Liquid-Liquid Equilibriums, Wiley, New York (1963) and
W. Malesinski, Azeotropy, Wiley New York (1965).
With modem computing facilities, constitutive equations for activity coefficients in
mixtures can be used for phase equilibrium calculations even if they are of rather
overwhelming complexity; see J. M. Prausnitz et al., Computer Caculations for Multicom-
ponent Vapor-Liquid and Liquid-Liquid Equilibria, Prentice-Hall, Englewood Cliffs (1980)
and S.1. Sandler, Chemical Engineering Thermodynamics, 2nd Ed., Wiley, New York (1988).
The whole question of the continuous description of gas-liquid equilibria is discussed
in several recent works. The simple case where Raoult's law applies is discussed by J. R.
Bowman, Ind. Eng. Chem. 41, 2004 (1949), and W. C. Edminster and D. H. Buchanan,
Chem. Eng. Prog., Symp. Ser. 6, 69 (1953). More recent literature is reviewed by S. K.
Shibata, S. I. Sandler, and R. A. Behrens, Chem. Eng. Sci. 42, 1977 (1987). Some of the
published literature fails to recognize that the shape of the distribution function in the
gas phase is different from that in the liquid phase [see, e.g., R. L Cotterman, D. Dimitrelis,
and J. M. Prausnitz, Ber. Bunsenges. Phys. Chem. 88, 796 (1984)] and should therefore be
read with care.
Chapter Ten
CHEMICAL EQUILIBRIA
NOTATION
a Activity
B Henry's constant atm
c Concentration kmol m- 3
CT Average molar density kmolm- 3
Cp Specific heat kcal kmol- 1 K- 1
D(L) Operator defined in equation (10.1.3)
fO Standard state fugacity atm
Gt Total free enthalpy kcal
gEX Dimensionless excess free enthalpy
g Vector of reference free enthalpies kcalkmol- 1
K Equilibrium constant vector
K( Equilibrium constant distribution
L Density of any extensive property
L( L distribution
M Number of independent reactions
m Initial concentration of amine kmolm- 3
n Total number of moles kmol 269
270 n( Number of moles distribution kmol
Chapter Ten n Number of moles vector kmol
N Total number of components
p Pressure atm
q Parametric vector kmol
r Steam/methane ratio
R Gas constant kcal kmol- 1 K- 1
T Temperature K
u Species label
VL Liquid specific volume m3 kmol- 1
v Fugacity coefficient
w Reaction label
x Extent of reaction vector kmol
XT Total extent of reaction vector kmol
y Mol fraction
y( Mol fraction distribution
z Parameter vector in Section 10.6
~ Pressure correction coefficient
f3( ). ~ distribution
p Vector defined in equation (10.1.10)
'T Activity coefficient
'TD Activity coefficient for dilute solution
fA. Chemical potential vector kcalkmor 1
p.( Chemical potential distribution kcal kmol- 1
a Stoichiometric coefficient matrix
u( Stoichiometric coefficient distribution
Subscripts
0 Initial value
j Speciesj
k Reaction k
T System as a whole
Superscripts
* At equilibrium
S For saturated vapor
K For nonreactive phase K
10.1. HOMOGENEOUS EQUILIBRIA IN
IDEAL AND DILUTE SOLUTIONS
(10.1.4) 271
272 Another useful operator is defined as follows for each reaction:
Chapter Ten
(10.1.5)
n* = Do + a . x* (10.1.7)
The general approach to the solution of this type of problem has been
discussed in Section 3.4; see equation (3.4.5). It is based on the definition of a
standard state, with respect to which the M-dimensional equilibrium constant
vector .K is defined. In this section, attention is restricted to the simple cases
where the activity coefficients are either unity (ideal solutions) or independent
of composition (dilute solutions), so that the constitutive equations for step (1)
assume a particularly simple form.
The very simplest case is where the system is a gaseous mixture at a pressure
low enough not only for the solution to be ideal, but also for all components to
behave as ideal gases. In this case, the constitutive equations for the chemical
potentials are
The kth component of IJ is zero if the kth reaction is equimolar. Equation (3.4.5)
reduces to
(10.1.12)
(10.1.13)
If only the solutes participate in the reactions, then equation (10.1.4) reduces to
(10.1.14)
n* = ~ n1 = no + IS' x* (10.1.15)
J
so that
(10.2.1)
where fO is the fugacity of the pure component at the same pressure and
temperature of the mixture, and in the same (in most cases, liquid) phase. The
value of f O is given by
(10.2.2)
where the superscript S identifies the saturation conditions of pure-component 275
gas-liquid equilibrium. If P is defined as
Chemical
Equilibria
(10.1.3)
(10.1.4)
which identifies g(T) with in the usual convention if the vapor pressure pS is
measured in atmospheres (see also Section 10.4). The equilibrium condition
becomes
(10.1.5)
1. Some simplified model for the activity coefficients can be used. In par-
ticular, it should be noted that the activity coefficients need not be known
individually, but only in the combination appearing in the operator 'IT;
this allows on occasion considerable simplifications of the constitutive
equations.
2. The eqUilibrium composition is sought by directly looking for the
minimum of free enthalpy in the composition subspace. If an equation
for gEX is available, this can be accomplished generally with numerical
techniques which are less cumbersome than those required for the solution
of the problem as formulated by equation (10.2.5).
n=no+a·x (10.1.7)
276 and therefore the additive term in equation (10.2.6) can be expressed in the form
Chapter Ten
n' g = Do' g + (u • x) • g
= Do • g + x· (u T • g)
= Do' g + X· D(g) (10.2.8)
The unknown term Do • g is constant and thus contributes nothing to the location
of the minimum of the free enthalpy in the reaction subspace. All other terms in
equation (10.2.6) can be expressed explicitly in terms of x.
Since attention is being restricted here to mixtures which do not exhibit
miscibility gaps, the free enthalpy surface over the composition space (and thus
a!ortiori its restriction to the reaction subspace) is concave upward everywhere,
and therefore only one minimum can exist; in fact, it is also the only extremal
point (there can be no saddle points and no local maxima). It follows that the
numerical search for the equilibrium point presents no major difficulties.
(10.3.1)
(10.3.2)
If N is the total number of components, then the best way to formulate the
problem is to seek a parametric solution, where the parameter is an N-dimensional
vector q, which represents the "initial number of moles" of the components in
the reactive phase, say (in a purely formal sense)
(10.3.3)
We note that each component of q does not represent the number of moles of
that component present in the reactive phase at equilibrium. The components of
q must of course satisfy the obvious condition
(10.3.4)
278 If q is regarded as known, one can write
Chapter Ten
n=q+a·x (10.3.5)
n* = n*(q) (10.3.6)
and
IJ.* = 1J.*(q) (10.3.7)
The condition of physical eqUilibrium now requires that, for every other
phase which may conceivably exist at equilibrium,
(10.3.8)
and, given constitutive equations for the chemical potentials in the nonreactive
phases, this can be transformed to
(10.3.9)
1. There is no way to satisfy all the equations. This implies that either one
or more of the phases assumed to exist at equilibrium does in fact not
exist, or vice versa.
2. The solution is likely to be nonanalytical, and hence elimination of q may
be computationally difficult.
10.4. ACfIVITIES
(10.4.1)
K = exp[-D(p,°)/RT] (10.4.2)
1T(a) = K (10.4.3)
Gases. The standard state is the pure gas regarded as an ideal gas. With
this, p, is simply g(T) as established in Section 10.1, and hence equations
(10.1.9)-(10.1.11) hold with p measured in atmospheres.
(10.4.4)
(10.4.5)
280 The chemical potential in the standard state is defined as
Chapter Ten
,.,.0 = geT) + RTln(B/ CT) (1004.6)
a = cr D {3 (1004.7)
(1004.8)
1T(C) = K (1004.9)
and hence the activity is unity to within the pressure correction term {3.
and second, the flue gas desulfurization process where a lime slurry is used for
absorbing sulfur dioxide:
(10.5.2)
Let 1 be the component which does not form a one-component phase (C0 2
and S02 for the two specific examples). In both examples, the activity of com-
ponent 1 is, at equilibrium, equal to the equilibrium constant of the reaction, i.e.,
it is a unique function of temperature:
at = K(T} (10.5.3)
This means that, at any given temperature, there is only one concentration of
component 1 in the reactive phase which, at equilibrium, is compatible with the
presence of both one-component phases. If the concentration is larger than this
value, the reaction will proceed to the right until the solid phase on the left
disappears, and vice versa. This has important practical consequences, such as
discussed subsequently for the two examples given above.
In the limestone decomposition case, coexistence of CaO and limestone is
possible at equilibrium only at one particular partial pressure of CO 2, That partial
pressure at room temperature is extremely low, in fact lower than the value in
atmospheric air; that is why limestone is a perfectly stable compound commonly
found in rocks. As the temperature is increased, the equilibrium CO 2 partial
pressure increases, and as soon as it exceeds the partial pressure of CO 2 in the
atmosphere a driving force for limestone decomposition appears. However, the
reaction is very slow, since it could only take place on the exposed surface of
the limestone. As temperature is increased further, the eqUilibrium CO2 partial
pressure reaches one atmosphere, and now a driving force exists even within the
limestone, so that decomposition will actually take place. At a temperature even
slightly larger than that, the equilibrium partial pressure of CO2 is larger than
one atmosphere, and therefore in a furnace open to the atmosphere the equilibrium
condition can never be realized until the limestone has decomposed completely
and the only solid left is CaO.
282 For the desulfurization process, the equilibrium concentration of S02 in the
Chapter Ten
liquid phase at room temperature is extremely low so that, in the presence of a
gas phase containing S02 in nonnegligible amounts, absorption continues and
lime is continuously transformed into gypsum, and equilibrium is reached only
when either all the lime has been consumed, or the partial pressure of S02 in
the gas phase has been reduced to the extremely low value corresponding to
coexistence of lime and gypsum. In practice, the process is run in such a way
that the first condition can never be realized (the entering flowrate of lime is
slightly in excess of the stoichiometric value needed to eliminate all the S02 from
the gas phase), and hence the process can in fact reduce the S02 content in the
gas to very low values. We note that, as long as the process is run, the slurry
contains both lime and gypsum, and hence the S02 concentration in the liquid
phase is kept at a constant low value. This means that there is no need to run
the slurry and the gas phases in countercurrent, but any flow arrangement is
equivalent to any other as far as the distribution of driving forces is concerned.
Indeed, the limestone process is always run with configurations other than the
countercurrent one.
More complex problems may arise when there is more than one reaction to
be considered. A good example is the steam reforming reaction of hydrocarbons;
for simplicity, consider the case of methane. The following two homogeneous
reactions are to be considered:
(10.5.4)
and
(10.5.5)
and the technical problem is typically that one wants to operate under conditions
where no solid carbon is formed. There are six components to be considered,
and these are numbered consecutively in the following order: CH 4 , H 20, CO,
H 2, CO 2, C. If the reactor is fed with a mixture of H 20 and CH 4 in a ratio r,
the initial total number of moles vector is
DTO = 1, r, 0, 0, 0, 0 (10.5.7)
Should solid carbon be present, its activity in the gaseous phase would be
unity, which corresponds to a negligibly small amount of carbon vapor (the
sublimation pressure of carbon is negligibly small). One may therefore assume
that, if no solid carbon forms at equilibrium, in fact no carbon at all forms; in
the terminology of Section 10.3, one chooses q to coincide with DTO. Reaction
(10.5.6) is tentatively excluded from consideration, and the actual number of
moles vector is expressed as
(10.5.8)
where Xl and X2 are the extents of reactions (10.5.4) and (10.5.5), respectively.
One now can solve this homogeneous equilibrium problem with the methodology
discussed in Sections 10.2 and 10.3 to yield the equilibrium activities of the 283
first five components; their value will, of course, depend on the value of the
Chemical
parameter r. Equilibria
Reaction (10.5.6) will in fact not take place provided the following condition
is satisfied:
(10.5.9)
and
C+C02 =2CO (10.S.U)
while the five components are numbered in the following order: MO, CO, M,
CO2 , C. Of these only 2, 3 and 4 may be present in significant amounts in the
reactive gaseous phase. Since solid carbon is guaranteed to be present at equili-
brium, the following condition is satisfied:
(10.5.1:!)
(10.5.13)
a = Pyv (10.S.14)
The three nonzero mole fractions in the gaseous phase are related to each
other by two additional equations. The first is simply the requirement that they
add up to unity:
(10.5.17)
The form of the second relationship depends on whether liquid metal does or
does not form. First we consider the case where it does not form. In this case,
for every gmole of metal in the reactive phase, there must also be one gatom of
oxygen, and hence
(10.5.18)
If some liquid metal does form, there are more gatoms of oxygen in the
reactive phase than there are gmoles of metal; however, the phase equilibrium
condition with the liquid metal now imposes
PY3 = P~ (10.5.19)
Since there are in both cases four equations relating the three nonzero mole
fractions, equations (10.5.15) and (10.5.16) can be satisfied, for any given tem-
perature, at only one particular pressure. Thus for the two subcases considered
one can solve the homogeneous reaction problem and obtain both the mole
fractions in the gaseous phase and the pressure.
In practice, it is best to first treat the case where no liquid metal is formed
and solve the problem described by equations (10.5.15)-(10.5.18). The calculated
pressure increases with increasing temperature, and so does the fugacity of the
metal vapor. For the special case where the metal is zinc, the left-hand side of
equation (10.5.19) increases with temperature more rapidly than the right-hand
side, so that at low temperatures no liquid zinc will form. It is therefore possible
to establish a minimum operating temperature (and a corresponding equilibrium
pressure) at which liquid zinc will form at equilibrium. If the reactor is run at
any higher temperature, liquid zinc is guaranteed to form, and can thus be
withdrawn. As it is withdrawn, new zinc oxide will be reduced, until reduction
is complete.
q = zm, m, 0, 0, 0, 0 (10.6.1)
and is thus identified by the value of one scalar parameter, z. This parameter
represents the ratio of the total number of moles of CO 2 (in both physically
dissolved and chemically combined form) in the liquid to the initial number of
moles of amine.
The reactions to be considered are
(10.6.5)
286 where Xt. X2 and X3 are the extents of reactions (10.6.2)-{10.6.4), respectively.
The problem is reduced to a homogeneous equilibrium problem, with three
Chapter Ten
independent reactions. The solution of this problem will yield the equilibrium
chemical potentials of all components as functions of the parameter z:
Jl.*=Jl.*(z) (10.6.6)
(10.6.7)
and, since CO 2 is the only component which can be present in both phases, the
phase equilibrium condition for CO 2 yields the partial pressure of CO 2 in. the
gas phase as a function of z. This constitutes essentially the required informa-
tion.
The second example is where there are two components which maybe present
in both phases, say CO 2 and H 2 S. To simplify the chemistry involved, attention
is restricted to the case where the liquid phase is an aqueous solution of a base
B, which is not alkaline enough for any significant amount of either S-- or CO)-
to form. The components to be considered are numbered in the following
order: H 2 S, CO 2 , B, BH+, HCO), HS-. With m again the number of moles per
liter of B initially present in the liquid phase, the parameter q is chosen in the
form
(10.6.11)
(10.6.12)
and the phase equilibrium conditions for CO 2 and H 2S will thus yield
the equilibrium partial pressure of the latter in the gas phase as functions
ofz.
10.7. CHEMICAL EQUILIBRIA IN CONTINUOUS MIXTURES 287
Chemical
An Algument to prove, that the Abolishing of Christianity Equilibria
in England, may, as Things now stand, be attend~d
with some Inconveniences, and perhaps, not produce
those many good Effects proposed thereby.
Jonathan Swift
Given a quantity L which is defined for each component [i.e., the function
L(u) is assigned], the operator D in equation (10.1.3) is generalized to
7T( w, L) = f L(u)u(w,u) du f
= exp[u( w, u) In L(u)] du (10.7.4)
Let us now consider the case where the mixture is an ideal gas. The chemical
potential distribution is
f
Chapter Ten
f3(w) = u(w, u) du (10.7.8)
Analogous equations could be developed for dilute solutions and for nonideal
mixtures. However, solving this type of equation for y*(u) may be extremely
difficult, even for the simple ideal-gas case, and thus the equilibrium composition
is best found by directly minimizing free enthalpy. The discussion in Section 10.2
concerning this technique is easily generalized. Equation (10.2.6) becomes
G.I RT = f n(u)g( T, u) du
The unknown term is of course the first integral. However, that term can be
expressed as follows:
Problems
10.1. If any fuel is burned to heat up a house, there is a risk that CO may form. This means,
as compared to the case when only carbon dioxide is produced, both a decreased efficiency (oxidation
of CO is an exothermic reaction) and a risk, since CO is poisonous. Discuss methods available for
minimizing the risk of CO production.
10.2. Lime is a comparatively expensive chemical to use for flue gas desulfurization, and it is
therefore proposed to use a limestone slurry as the absorbing medium. Discuss the chemistry involved
and establish the eqUilibrium conditions for such a process. Can the sulfur dioxide mole fraction in
the gas phase still be reduced to a negligible amount?
10.3. Does Duhem, in the quote of Section 10.6, refer to ammonium carbonate or to ammonium 289
carbamate?
10.4. In an initial analysis of a methanol synthesis process, the following chemical reactions Chemical
have been considered: Equilibria
co + 2H2 = CH 3 0H
CO + 3H 2 = CH. + H 20
CO + H 20 = CO 2 + H,
2CO = CO,+C
CO 2 + 4H2 = CH. + 2H 20
CH 3 0H = C + H 20 + H2
4CO + 2H 20 = CH. + 3CD 2
LITERATURE
ELECTROCHEMISTRY
NOTATION
(11.1.1)
c*=(1-a)m (11.1.2)
and
c! = c~ = am (11.1.3)
(11.1.4) 293
294 where K is the concentration-based equilibrium constant for reaction (11.1.1).
Chapter Eleven (As discussed in Chapter 10, K is not a true constant since it contains activity
coefficients; however, this is irrelevant in the present context.) The important
point is that, as m approaches zero, the solution of equation (11.1.4) approaches
a = 1, i.e., provided the solution is sufficiently dilute, the electrolyte is completely
dissociated. The same conclusion is reached also in the general case of an
electrolyte which is not uni-univalent. The dissociation reaction can be written as
(11.1.5)
(11.1.7)
(11.1.8)
It is easy to convince oneself that the equilibrium degree of dissociation 295
approaches unity as pressure becomes very low and temperature very high-which
Electrochemistry
are the conditions at which ideal-gas behavior is expected. Hence, if one assumes
the gas to be completely dissociated, the observed equilibrium p- V - T behavior
will indeed correctly approach the ideal-gas behavior; it would not if one assumed
the gas to be undissociated, since in the limit the actual number of moles would
be twice that assumed. As temperature is lowered and/ or pressure increased,
deviations from ideal-gas behavior would be observed. These could be used to
infer the "true" degree of dissociation, if one is willing to assume that in fact
the mixture still behaves as an ideal gas-but there is no guarantee that that is
the case. Alternately, one could regard the gas as always completely dissociated
and ascribe all observed deviations to the fugacity coefficient (this is the approach
of the theory of strong electrolytes). Third, if one has some independent means
of ascertaining the actual degree of dissociation, "true" fugacity coefficients could
be extracted from the p- V - T data. This approach is hardly feasible in the case
of electrolytic solutions.
We now note that the discussion in the above paragraph would apply to any
gas capable of dissociation, say for oxygen, where one could consider its dissoci-
ation into atomic oxygen. This is never done, because the pressure and temperature
at which molecular oxygen approaches the behavior of an ideal gas are much
less extreme than those at which it dissociates significantly into atomic oxygen.
The difference is not qualitative but simply quantitative; the equilibrium constant
for the oxygen dissociation reaction is extremely small. The analog of N 20 4 is a
strong electrolyte; the analog of molecular oxygen is a weak electrolyte. Salts are
invariably strong electrolytes; acids and bases may be both strong and weak.
Let us first consider the theory of strong electrolytes, in particular the
problems imposed by the condition of electrical neutrality. This condition requires
that, at any point and at any time, the total concentration of positive charges
must equal that of negative charges. A rationale for this condition is discussed
in the next section. The important point is that the condition of electrical neutrality
makes the chemical potential of an ion unaccessible to measurement. The deriva-
tive 5Gt /5nj can never be measured, since it is experimentally impossible to have
two solutions which differ only in the number of moles of one particular ion; at
least one of the two would violate the condition of electrical neutrality. However,
from a formal viewpoint the concept of the chemical potential of an ion is
perfectly legitimate.
We shall examine again the simple case of a solution for which only
reaction (11.1.1) needs to be considered. The equilibrium condition can be
written as
(H.t.tO)
296 with the standard state chosen so that, at infinite dilution, the activity coincides
with the concentration measured in kInol m- 3 :
Chapter Eleven
(11.1.11)
(11.1.12)
(11,1.13)
It is now useful to define the following average values for the two ions:
(11.1.14)
(11.1.15)
(11.1.16)
The geometric average is chosen for the concentration and the activity
coefficient, since these contribute to the chemical potential through their
logarithms. With these definitions, equation (11.1.9) becomes
(11.1.17)
which shows that the average activity coefficient of the ion pair is accessible to
measurement, though the two individual ones are not. In the case of an electrolyte
which dissociates according to reaction (11.1.5), the averages are defined as
follows:
(11.1.18)
(11.1.19)
(11.1.20)
(11.1.21)
Since only the average activity coefficient of an ion pair is accessible to 297
measurement (and of pragmatic interest), one can arbitrarily assign the value Electrochemistry
unity to the activity coefficient of one particular ion (the hydrogen ion is the
usual convention), and then define individual activity coefficients based on such
a convention. For instance, the activity coefficient of the chlorine ion is simply
the average coefficient for dissociated hydrogen chloride. Once this is established,
the activity coefficient of the sodium ion is such that, when multiplied by that of
the chlorine ion, it gives the square of the average coefficient of dissociated
sodium chloride; and so on. Values of individual activity coefficients of ions
reported in the literature are based on this convention.
Now let us turn our attention to the question of the behavior of the solute
in a dilute electrolytic solution. Again considering the simple case of an uni-
univalent electrolyte, the mole fraction Y of the solute is, within the first-order
approximation, proportional to its concentration:
Y = m/cs (11.1.22)
where Cs is the molar density of the solvent (55.5 kmol m- 3 in the case of water).
If'Ts is the activity coefficient of the solvent, the Gibbs-Duhem equation can be
expressed in the form
(11.1.25)
(11.1.U)
where the quantities Cj are the concentrations of the ions and the Zj the correspond-
ing electrovalences (for the case of a solution containing only a uni-univalent
electrolyte, 1= m). The Debye-Huckel model results in the equation
(11.1.27)
(11.1.28)
where the first term on the right is the Debye-Huckel one. The interaction
parameters are often expressed as follows:
(11.1.29)
with the terms on the right regarded as constant for any given ion.
Average activity coefficients of ion pairs are accessible to measurement
through a variety of techniques: solubility measurements (in the case of elec-
trolytes which are solid if pure, as indeed is the case with most salts), vapor
pressure measurements (in the case of volatile electrolytes such as Hel), measure-
ment of the electromotive force of electrochemical cells (i.e., of the val~e E*
discussed in Section 3.5), and nonequilibrium measurements such as diffusion.
A specific case is discussed here, that of AgI03 • If a solution of AgI0 3 is in
equilibrium with the pure solid salt, the chemical potential of AgI0 3 in solution
is equal to the free enthalpy density of the pure solid, say
(11.1.30)
Even if the value of'O is known, that of p.~ is not, so equation (11.1.30)
may be rewritten as
(11.1.31)
with U an unknown constant. Let S be the solubility of AgI0 3 , i.e., the number 299
of moles of salt dissolved into the solution at equilibrium; S is measurable. With Electrochemistry
the formal assumption of complete dissociation, one obtains
(11.1.32)
and hence
(11.1.33)
Now suppose the solubility is low enough that the resulting ionic strength
is within the limits of validity of the Debye-Huckel model. Equation (11.1.33)
can be expressed as
(11.1.35)
c=S+m (11.1.36)
I=!(S+m) (11.1.37)
The Poisson equation for the spatial distribution of the electrical potential
q, is
where Q is the local electrical charge density (coulomb m -3) and E is the dielectric
constant (coulomb V-I m- I ). The Faraday constant F is the charge of a
kequivalent of ions, i.e., the charge of one kmole of a univalent ion. Hence the
local charge density is given by
(11.2.2)
(11.2.3)
The value of F is 9.65 x 107 coulomb per kequivalent. The dielectric constant
of aqueous electrolytic solutions is of the order of 10-9 coulomb V-I m- I • Hence
the coefficient F / E in equation (11.2.3) is at least 1017 V m per kequivalent.
Now if the sum appearing in equation (11.2.3) is of the order of, say, to- 1O
kequivalent per m\ then such a value would be extremely small as compared to
the values of any term in the sum-unless the ionic concentrations are so small
as to be of no practical importance whatsoever. It follows that, if the concentra-
tions of all the ions except one are known, the latter could be calculated by
assuming that the sum is zero, i.e., one would make use of the condition of
electroneutrality, as discussed in the previous section. However, the right-hand
side would still be of the order of t07 V m- 2 , i.e., a very steep curvature of the
electrical potential distribution could exist. It follows that, while the condition
of electroneutrality can in fact be regarded as universally true (except near
electrode-solution interfaces), the electrical potential does not have a Laplacian
distribution (i.e., divgrad q, is not zero). The electroneutrality condition is violated
significantly [say the sum appearing in equation (11.2.3) is of the order of
to-I kequivalent per m 3 ] when divgrad q, is of the order of tO I6 V m -2. Since the
(11.2.4)
and of course the same equation applies also to free enthalpy. Hence, the
electrochemical potential of the jth ion is given by
(11.2.5)
where the second term is as legitimate a concept as the first, since both imply
only consideration of a differentially small variation of nj, which is not forbidden
by the electroneutrality condition since the latter holds in the sense discussed in
the previous paragraph.
Now we consider a situation where there are finite gradients of the
electrochemical potentials, so that we expect finite diffusive fluxes of the ions.
Let Nj be the total flux of the jth ion, which includes the diffusive flux as well
as the convective flux,
(11.2.6)
where v is the average velocity discussed in Section 7.3. The vector of current
intensity is
(11.2.7)
(11.2.8)
In order to proceed, one needs to write constitutive equations for the diffusive
fluxes. The theory of transport processes in electrolytic solutions is generally
developed by neglecting the possibility of direct coupling at the constitutive
equations level (as will be seen, strong coupling arises anyhow), so that the flux
of the jth ion is given by
(11.2.9)
where the quantities Uj are called the mobilities. Substitution into equation 01.2.8)
gives
(11.2.10)
302 Let us first consider the case where there is no net electrical current flowing
through the solution (electrochemical cells are thus excluded from consideration).
Chapter Eleven
If the concentrations of the ions are not uniform in space, the second term on
the right-hand side of equation (11.2.10) is nonzero, and hence also the first term
must be nonzero. In an electrolytic solution, when nonzero concentration
gradients are present, a gradient of electrical potential may develop. The physical
interpretation of this conclusion can be better understood by considering equation
(11.2.7) which, for the case of zero intensity, yields the condition
(11.2.11)
If, for instance, the solution only contains a strong uni-univalent electrolyte
MX, then for this case equation (11.2.11) simply requires the fluxes of the two
ions to be equal. The condition of electroneutrality requires the concentrations
of the two ions to be the same everywhere, and hence so are the concentration
gradients. If the diffusivities of the two ions are not equal to each other, the first
term on the right-hand side of equation (11.2.9) would be different for the two
ions, and hence the two fluxes can only be equal if a gradient of electrical potential
develops which slows down the flow of the ion with a higher diffusivity, and
accelerates that of the other one. This shows that, even neglecting direct coupling
at the constitutive equation level, strong coupling between the diffusive fluxes of
different ions arises anyhow.
The relationship between diffusivities and mobilities can be established as
follows. Equations (11.2.9) can be rewritten as
(11.2.12)
(11.2.13)
which, for solutions which are dilute enough for activities to coincide with
concentrations, reduces to
(11.2.14)
(11.2.15)
tj = p2ZJUJ'j/il (11.2.16)
which, in the case where there are no concentration gradients, can be interpreted 303
as the fraction of the total current carried by the jth ion. The definition, of course,
Electrochemistry
is. still legitimate even when there are concentration gradients, but the interpreta-
tion is more vague.
Experiments carried out with alternating current afford a means of measuring
the value of n. For dilute solutions, the values of the mobilities can be estimated
from equation (11.2.14), and hence the measurement of n yields an estimate of
the order of magnitude of the ionic concentrations. It is this type of measurement
which leads to the consideration of weak electrolytes, for which the measured
electrical conductivity is very significantly less than what one would estimate
from the assumption of complete dissociation. Hence the conclusion is reached
that such electrolytes are only very weakly dissociated, resulting in ionic con-
centrations several orders of magnitude smaller than the amounts of electrolyte
present in the solution, even for very dilute solutions.
Appendix
(11.3.3)
(11.3.4)
is very small, e.g., less than 10-2 kmol m- 3 • The equilibrium constant Kp is called
the protonation constant and, as will be seen, it is also defined, with appropriate
qualifications, for bases and salts.
Since concentrations of different species may have very different orders of 305
magnitude, it is useful to work with their logarithms. For the special case of the Electrochemistry
hydrogen ion the definition of pH is
(11.3.5)
where the minus sign is chosen so that values of pH are almost invariably positive.
The pK of the acid is defined as
pK = -logKp (11.3.6)
[H+] = XI + X3 (11.3.8)
[OW] = X3 (11.3.9)
[X-] = XI (11.3.10)
an equivalent set of linear equations which reduce the composition space to the
reaction subspace. The algebra involved is often simpler with the second approach.
The equations which identify the reaction subspace are linear in the con-
centrations, but the equilibrium equations are not; conversely, if the logarithms
of the concentrations are used, the equilibrium equations become linear, but the
former ones become nonlinear. Suppose that, for the example at hand, the extent
of reaction approach has been chosen, and consider the case where pK = 4. The
two equilibrium equations become
(1l.3.13)
and
(11.3.14)
306 This corresponds to a fourth-order polynomial, and the case considered is
sufficiently simple for the solution to present no particular difficulties. We note,
Chapter Eleven
however, that the fact that the coefficients appearing in the two equations differ
by ten orders of magnitude introduces some stiffness even in this very simple case.
The method of approximate solution which is easiest to follow is to draw a
"characteristic plot" of the logarithms of the concentrations of interest vs. pH,
i.e., to seek a solution that is parametric in pH. Consider such a plot shown in
Figure 11.3.1. The lines for H+ and OH- are immediately obtained as simple
straight lines. Now we let a be the degree of dissociation of the weak electrolyte
(which is expected to be small), say
(11.3.15)
which gives the straight line on the left of Figure 11.3.1. We note that 10g[OH-] =
pH - 14 and hence, provided pK is significantly less than 14, as long as equation
(11.3.17) holds it will result in a value of [X-] significantly larger than [OH-].
Hence the intersection of the 10g[X-] and 10g[H+] lines, that indeed takes place
at a pH significantly less than pK, is the solution of the problem since the
electroneutrality condition is (approximately, but very closely) satisfied at that
point. The intersection is given by
2pH = pK - log m (11.3.18)
u
CI
pH::V2 (pK-Iogm)::2.25
~
logm
-1
-3
-s
-7
0 2 4 6 8 10 12 14 pH
(11.3.19)
(11.3.20)
which is called the protonation reaction of the base, with equilibrium constant
Kp given by
(11.3.21)
If Kb is 10-4 kmol m -3, so that in a sense the base is as weak in this example
as the acid was weak in the previous one, the pK would be 10. This shows how
the distinction between weak bases and weal acids is somewhat arbitrary. One
could regard as a base any weak electrolyte with a pK in excess of 7, and as an
acid anything with a pK less than 7, water being left to represent the borderline;
this is, however, totally arbitrary.
Again a characteristic plot such as in Figure 11.3.2 is useful. The degree of
dissociation a can be introduced again, with [B] = m(1- a) and [BH+] = rna,
so that the equilibrium condition for reaction (11.3.20) becomes
u
Ol
pH=7+1/2 (pK+logm)=11.75
~
log m
-1
-3 BH+
-5 :
I
I
10<:
:0.
-7 I
I
0 2 4 6 8 10 12 14 pH
(11.3.24)
(11.3.25)
which is the exact analog of reaction (11.3.19), i.e., the dissociation reaction of
a weak base. In the presence of the cation of a strong base, the anion X- behaves
as a weak base.
Instead of reaction (11.3.25), one could consider the equilibrium of reaction
(11.3.3). With this, the problem would be set up exactly as in the case of a weak
acid, except that the electro neutrality condition is now
(11.3.26)
(11.3.27)
(1l.3.28)
and so on. For phosphoric acid, the three successive pK values are 2.23, 7.21,
and 11.32. In principle, in a solution containing m kmol m- 3 of H3X, there are
thus four chemical equilibria to consider: the three acid dissociations and the
water dissociation. This is equivalent to a sixteenth-order polynomial equation,
containing four coefficients the values of which span 12 orders of magnitude.
This is an extremely stiff nonlinear problem, and an approximate preliminary
solution is not only desirable but indispensable.
Again, it is useful to consider a solution scheme which is parametric in the
pH. Let ao, ... , a3 represent the fractions of m present in the form of
H 3X, ... , X---. The following three relationships between the quantities a are
easily established:
(1l.3.l9)
which, together with the condition that the quantities a sum to unity, gives the
desired parametric solution; this is plotted, for the case of phosphoric acid, in
u
t7I
.£
-1
-3
-5
-7
0 2 4 6 8 10 12 14 pH
FIGURE 11.3.3. Characteristic plot for the salt of a weak acid and a strong base.
310 Figure 11.3.4. It can be observed that at no value· of the pH is the value of more
than two quantities a nonnegligible; hence in every pH range the acid can in
Chapter Eleven
fact be analyzed as a monofunctional one. If a calculation is conducted for an
m value of 0.1 lanol m- 3 (or larger), we can start by assuming that there is only
H3X and H2X-, and indeed the calculation confirms this hypothesis. In this sense,
phosphoric acid can be regarded as a weak electrolyte. However, if the same
calculation is performed at a concentration level of 10-4 lanol m-3, the same
hypothesis leads to a paradox, and the solution actually results in a pH range
where the only species of interest are H2X- and HX--. There is no undissociated
phosphoric acid at this low concentration, i.e., phosphoric acid behaves as a
strong electrolyte. This confirms the earlier statement that the distinction between
strong and weak electrolytes is somewhat arbitrary, and the classification of any
given electrolyte depends in some measure on the level of total concentrations
under investigation.
Indeed, the above considerations apply to any solution of a weak acid or
weak base. For instance, in the case of HX discussed at the beginning, equation
(11.3.18) in fact holds only as long as pH is less than pK, or equivalently, as
long as log m is larger than -pK. At lower concentrations, the acid is in fact
completely dissociated (i.e., it behaves as a strong electrolyte), and pH = -log m.
In contrast with this, the anion X- of a salt MX behaves always as a weak base;
equation (11.3.23) holds down to log m = -pK. At even lower concentrations,
water itself becomes the electrolyte which determines the acidity of the solution,
and pH = 7. (This is a general result: whenever the total concentration of elec-
trolytes in an aqueous solution is less than 10-7 lanol m- 3, their presence can be
entirely neglected. However, this is an exceedingly low concentration, which is
seldom encountered except in the laboratory.)
The shape of the curves in Figure 11.3.4 is related to the fact that the
successive pK values of the phosphoric acid dissociations differ significantly
from each other. While this is always true in the case of polyfunctional inorganic
acids, it is not in the case of polyfunctional organic acids. For the latter, the full
1.0
OV i
0.5
4
r PH =1I2(pK-logm) i
weak electrolyte
2
-10 -8 -6 -4 -2 o
., , ,., ,
pH
14 pH=7+1/2 (pK+logm) j
~U.
12
-10 -8 -6 -4 -2 o logm
pH
11 C. . .
pH =7+1/2 (pK+ log m);
",,'~.
I
9 pH = 7; dominated
by water
7 I-~ _ _ _ _ _"'-
-10 -8 -6 -4 -2 o logm
FIGURE 11.3.S. pH vs. concentration plots: (a) a weak acid; (b) a weak base; (c) a salt
of a weak acid and a strong base.
313
u
.9 rPH=PK \og[M+] r\Og(2m.) Electrochemistry
-1
-::::-------~---------------~-----------------
-3
-5
pH
8
pH= pK I
4 ---------------+-~---------
1
I
I
1
2 1
",I
o.i
I
o
log (2m·)
-10 -8 -6 -4 -2 o
FIGURE 11.3.7. pH vs. concentration for a buffer solution.
314
u 1+~
Chapter Eleven C1> logm
('PH=PK+I09 1-/3
.2 ("IOg(2m·)
-1
-3
BH+
-5
><:
0.,
-7 ,
I
0 2 4 6 8 10 12 14 pH
FIGURE 11.3.S. Characteristic plot for a buffer solution with some base added.
a weak base B is added to the MX/HX solution, and (3 is the ratio m/m*. The
characteristic plot is sketched in Figure 11.3.8, and the pH is calculated as
and is thus seen to differ little from the pH of the pure buffer as long as {3 is
significantly less than unity. We note also that the pH depends on {3, but not on
the basicity of the third electrolyte, B.
Since in solutions of mixed electrolytes the concentrations of both the
hydrogen ion and the hydroxyl ion are negligible, the calculation of their composi-
tion can be set up as a standard chemical equilibrium problem, and only ionic
reactions which do not include H+ or OH- need be considered. The cases
discussed in Section 10.6 are of this type. There is no problem of stiffness of the
resulting equations, since all components involved are present in appreciable
concentrations. Once the composition has been obtained, the pH can be calculated
from the equilibrium of any ionic reaction involving two ions whose concentration
has been determined as well as H+. Let us consider, for instance, the first example
in Section 10.6. Once the chemical equilibrium problem has been solved, the
CO:;-- and HCO:;- concentrations are known. The pH can then be calculated from
the equilibrium condition of the reaction
(11.3.31)
One does not find in the circuit all the heat developed by
chemical action ... part of it apparently serves to overcome
some resistance, on the exact nature of which I do not dare
to advance any hypothesis. One must therefore admit
that part of the motive power arising from the chemical agents
does not contribute to the production of that useful
electrical work one tries to realize in electromotors.
P. A. Favre, 1854
By electrochemical reactions we mean those reactions which can only take 315
place when a finite lliectrical current is flowing through the electrolytic solution. Electrochemistry
In particular, the electrode reactions are those which take place at the interface
between the solution and an· electrode. Such reactions need not be electrically
neutral, since the electric charge liberated (or absorbed). by them can be carried
away by the electrode through the external electrical circuit of the cell. Formally,
the electroneutrality of these reactions can be maintained by considering the
electrons themselves as reactants and/ or products.
Electrode reactions can be classified in two main categories. The first is that
of redox reactions, which liberate or absorb one or more electrons, but do not·
exchange metal ions with the electrode. The stoichiometry of a redox reaction
can be written as follows:
(ItA.I)
(ItA.2)
The second category of electrode reactions comprises those where metal ions
are actually exchanged with the electrode. They can always be expressed as a
sequence of redox reaction plus a reaction of the type
M = MZ++ze (ItA.3)
where z is the (positive) electrovalence of the metal ion. We note that, at any
one time, the overall condition of electroneutrality of the solution needs to be
respected, and hence for any electron released by the solution to an electrode,
one must be released by the other electrode to the solution. Furthermore, except
in a layer of molecular size near the metal-solution interfaces, the electroneutrality
condition must be satisfied everywhere in the solution. .
Electrons and metallic ions are the only species which can be exchanged
between the solution and the electrodes. In this sense, the electrode interface is
an ideal semipermeable membrane, which allows only these two species to
permeate. (The statement should be qualified in the case of ~ydrogen, which can
in fact.permeate some metals.) The electrode-solution equilibrium conditions
are therefore easily established by requiring the electrochemical potential of the
permeating species to be the same in the two phases. Furthermore, the electrode
has a fixed composition, and hence the electrochemical potentials in the electrode
phase are simply given by
and
(llA.5)
(11.4.6)
where the subscript S identifies the solution. Hence the equilibrium condi-
tion is
where the term cf>~/s is called the Galvani potential and, at any given temperature,
is a constant characteristic of the electrode. It should be noted, however, that
the electrical potential difference between an electrode and a solution can never
be measured: in order to carry out a measurement, one would necessarily need
another metal to pick up the solution potential, and this metal would act as an
electrode and establish its own electrical potential difference with the solution.
It will be seen later that this difficulty is circumvented by arbitrarily assigning
the value zero to one particular electrode-solution pair.
The junction between two (different) metals is now treated. The only species
which can permeate through the junction are the electrons, and thus the electrical
potential difference between two metals is, at any given temperature, a constant
depending only on the nature of the two metals. It is easy to convince oneself
that this has an important consequence. Given a chain of several different metals,
the equilibrium electrical potential difference between the first and the last is the
same as would exist if the first and last metal were directly linked to each other.
It follows that one need not worry, at equilibrium, about the details of the external
circuit of an electrochemical cell; only the nature of the two metals constituting
the electrodes is of importance, and these two can be regarded as being directly
linked together. Quite obviously, these considerations do not apply to nonequili-
brium conditions, Le., when a finite current is flowing through the metals. Suffice
it to state that the electrical potential within a given single metal is not constant
when a current is flowing. The argument is also restricted to an isothermal metal
chain; thermocouples and Peltier effect coolers work on the basis of the fact that,
in a nonisothermal metal chain, potential differences develop which are not
balanced when the chain is closed into a loop.
Let us now consider the case of an electrode at which a redox reaction may
take place. The only permeable species are the electrons, and hence the equili-
brium condition is simply the equality of the electrochemical potential of the
electron in the metal and in the solution. This leads to the equation
(11.4.8)
(1l.4.9)
since ES'/Pt has been assigned the value zero. If the experiment can be performed
under conditions where the SIS' electrical potential difference is zero, the
measured value of E* is called the standard electrochemical potential of the MIS
pair.
Since the Sand S' solutions are different, current (though microscopically
small under the conditions of the experiment) can flow between them only by
actual flux of ions, and this could give rise to an SIS' electrical potential difference
due to the diffusive coupling discussed earlier. The problem is serious, since one
of the ions involved is the hydrogen ion, which has a much higher mobility than
that of most other ions. In addition, if the two solutions are brought into direct
contact, the irreversible neutralization of metal ions by molecular hydrogen could
take place. Therefore, Sand S' need to be kept separated, and this is usually
accomplished by what is called a salt bridge. A salt bridge is a tube containing
a gel in which a salt is dissolved whose anion and cation have very close mobilities.
With this device, the SIS' electrical potential difference can be made negligibly
small as compared to the other potential differences involved.
Once the standard electrochemical potential of an MIS pair has been estab-
lished, the value of E* for a cell with two different electrodes in the same solution
is obtained by the difference. It is important to realize that two different conven-
tions concerning the sign to be assigned to standard electrochemical potentials
are found in the literature. Of course, the whole discussion above is only concerned
with the equilibrium behavior of electrochemical reactions.
318 EXAMPLES AND PRO~LEMS
Chapter Eleven
Problems
11.1. Draw the characteristic plot, and a plot of pH vs. In, for ammonium sulfate.
11.1. Consider solutions of potassium carbonate and potassium citrate, with m = 0.1 kmol m-3.
A solution of 0.2 kmol m-3 HCI is slowly added to 10-4 m3 of the solutions considered. Draw a plot
of pH vs. m3 of solution added.
11.3. Estimate the electrical conductivity (for AC current) of solutions of sodium chloride,
sodium acetate, and ammonia, as a function of m.
11.4. It has been observed that the measured electrical conductivity of an electrolyte solution
depends on the frequency of the applied AC current. Describe the possible reasons for this, and a
method for extracting the true conductivity from the data.
11.5. Consider the first example in Section 10.6. Which condition should the pK of the amine
satisfy for the carbonate ion concentration to be negligibly small? Can an analogous condition be
determined for which the bicarbonate ion concentration is negligibly small?
LITERATURE
This chapter is heavily indebted to the notes for a course in electrochemistry which
Prof. F. Gioia gave for several years in the 19708 at the University of Cagliari, Italy.
Textbooks on electrochemistry abound, and most of them cover the material presented
here (and much more).
Chapter Twelve
POLYMERS
GIUSEPPE MARRUCCI
University of Naples
Naples, Italy
NOTATION
d Diameter of rods m
E Potential energy kcal kmol- I
F Force N
G Free enthalpy kcaIkmol- 1 319
320 G Elastic modulus (Section 12.3) Nm- 2
Chapter Twelve g =G/RT
g* Dimensionless G per unit volume
H Spring constant Nm- I
H M1X Enthalpy of mixing kcalkmol- I
J Total flux of dumbbells m- 2 S-I
JD Diffusion-induced contribution to J m- 2 S-I
JE Elastic-induced contribution to J m- 2 s- 1
Jv Velocity-induced contribution to J m- 2 S-I
k Boltzmann constant kcal molecule-I K- I
L Curvilinear tube length m
1 Rod length m
M Molecular weight kgkmol- I
Mc Critical molecular weight kgkmol- I
N Number of "tube" random walk steps
n Number of Kuhn segments
nJ Number of moles of J component kmol
p Order parameter
pOs Osmotic pressure atm
R Gas constant kcal kmol- I K- I
r End-to-end vector m
S Entropy kcal kmol- I K- I
So Cross-sectional area of unstretched sample m2
S' Partial molar entropy kcal kmor l K- 1
s'( Constitutive function for S' kcal kmol- I K- I
T Temperature K
T* Equilibrium phase transition temperature K
Time s
u Unit vector
V Free volume m3
VEXCL Excluded volume m3
v Velocity ms- 1
W( Distribution function m- 3
X Ratio of polymer to solvent volume
y Ratio of polymer to monomer volume
x,y,z Components of r m
YJ Mole fraction of component J
a Expansion ratio
Expansion ratio in J direction 321
Magnitude of velocity gradient Polymers
Shear magnitude
Angle
Viscosity kgm-1s- 1
Viscosity increment due to polymer kgm- I S-I
Chemical potential of solvent kcal kmol- I
Chemical potential in standard state kcalkmol- I
Viscosity of solvent kgm- I S-I
Intrinsic viscosity m 3 kg- 1
Friction coefficient Nsm- I
u Axial stress Nm- 2
(J' Extra stress tensor Nm- 2
Components of extra stress tensor Nm- 2
Relaxation time s
4> Volume fraction
4>J Volume fraction of component J
4>* Limit volume fraction for concentration
solution
4>1 Limit volume fraction for two-phase system
4>2 Limit volume fraction for total anisotropy
X Interaction parameter
Superscripts
MIX Of mixing
SW Of swelling
EL Elastic
Operators
H H H H
I I I I
.. ·-C-C-C-C-···
I I I I
H H H H
the actual polymer being obtained when the basic unit, -CH 2 - , is repeated
thousands or tens of thousands of times.
Such a seemingly dull chain is in fact capable of assuming an astronomically
large number of different conformations (or shapes), as discussed below. The
possibility of a very large number of different molecular configurations is what
sets apart polymers from ordinary low molecular weight materials, the molecules 325
of which have an essentially fixed shape, capable of only minor distortions. Polymers
To understand the possibility of a large number of conformations, one should
remember the tetrahedral structure of the bonds of the carbon atom. Thus, if
three consecutive carbon atoms are placed in the plane of the paper (see Figure
12.1.1), the fourth one can move along the circle sketched in the figure without
altering bond angles and distances. A more detailed analysis shows that, along
the circle, there exist three energy minima (corresponding to one trans and two
gauche conformational isomers), and that the energy barriers between them are
small enough to be easily overcome by thermal energy. The existence of three
alternative positions for each consecutive carbon atom implies that a chain made
up of n such atoms can assume a number of different configurations of the order
of 3", which is indeed astronomically large already for n of order 100.
This conclusion, in its qualitative implications, is by no means altered if a
different "chemistry" is considered. For example, polystyrene will differ from
polyethylene insofar as some conformations will be more or less impeded by the
bulky benzene groups. Nevertheless, an enormous number of them will still
remain available. Similarly, the presence of double bonds, by prohibiting rotation
around them, will decrease the degrees of freedom to some extent. A chain like
that of polybutadiene, however, although containing a double bond every four
carbon atoms, still remains extremely flexible (the word flexible is used here to
indicate the capability of the chain to change its conformation by rotations around
bonds; it has nothing to do with the flexibility of, say, an elastic beam). Flexible
chains in the liquid state (or in the rubbery state, as will be seen later) will in
fact continuously change their conformation as a consequence ofthermal motion.
We shall see in the following the far-reaching effects of this peculiar property.
Polymers which have a single, fixed conformation are by far the exception.
These rigid polymers are also of interest, however. They will be discussed in
Section 12.6.
Returning to Figure 12.2.1, we may define a local orientation of the chain
by the vector which links alternate (not consecutive) carbon atoms. Thus, starting
from the left, the first and third atoms in the figure define a specific orientation
of the chain, U 1 (which is horizontal in the figure). The second and fourth atoms,
depending on the position of the latter on the circle, define in general a different
orientation U2. Of course, for a given Ulo U2 is restricted to a range of values. If
additional atoms are considered, however, soon the orientational correlation is
completely lost. In other words, if I and J are not too close, UJ and UJ are
randomly oriented with respect to each other. (If the fourth atom in Figure 12.2.1
w)
,,//,
" ..;/'/
/' / /
FIGURE 12.2.1. The carbon atom backbone ,,"
I
/1 / '
,
of a polymeric chain. After placing the first I
I
I
,
I
,
"" ,,
I
(12.2.1)
(12.2.2)
Equation (12.2.1) describes the probability that the chain may be found in
the neighborhood of a given value of the end-to-end vector r. Therefore, as long
as the only variable considered is r, one may associate with it (to within an
arbitrary additive constant) the entropy S,
S(r) = kin W(r) = -3kr2/2nb 2 (12.3.1)
328 where k is the Boltzmann constant. Correspondingly, and consistently with the
fact that in the ideal chain there are no energy effects, the free energy is given by
Chapter Twelve
(12.3.5)
We now consider any chain segment in the network between two consecutive
cross-links. If x, y, z are the components of the end-to-end vector before the
deformation has been applied, after the deformation we may write
(12.3.6)
(12.3.8)
We are now ready to calculate the free energy per unit volume of a deformed
rubber. By ensemble averaging equation (12.3.2) and substituting for (r2) from
equation (12.3.8), we obtain
(12.3.9)
where c is the number of chains per unit volume forming the network.
It should be noted that n does not appear explicitly in equation (12.3.9). 331
Thus, as shown in the following, the assumption that all chains have the same
Polymers
value of n is unnecessary. As long as equation (12.3.7) remains valid for any
subset of chains having given values of n[, equation (12.3.9) is obtained, with
the corresponding CI in place of c, for the Ith contribution to free energy. Summing
all these contributions, equation (12.3.9) with the overall concentration C is again
obtained. We note, however, that the average value of n appears indirectly in
the result, through C itself. Indeed, imagine adding further cross-links to the
network, thus ·reducing the average value of n. The number of chains per unit
volume correspondingly increases. In fact, the prefactor in equation (12.3.9)
essentially depends on cross-link density and, weakly, on temperature. We shall
see shortly that this prefactor is the modulus of rubber elasticity.
An important assumption embodied in the result of equation (12.3.9) is that
of affinity of the deformation. When writing equation (12.3.6), we have assumed
that the chain end-to-end vector deforms as if it were imbedded in the continuum,
i.e., that it deforms affinely with the macroscopic deformation. Since equation
(12.3.7) rather than (12.3.6) has been used to obtain our result, it is only required
that the affinity assumption holds on the average. Even for the average, however,
affinity is by no means assured, and different possibilities can be, and have been,
envisaged. Here we ignore all such complications and proceed to show some
results of rubber elasticity theory in its basic form.
Stresses are obtained from equation (12.3.9) by equating the work done by
them upon deforming the material to the corresponding change in free energy.
(This is essentially why the theory considered is one of elasticity, in the sense
used in previous chapters, so that mechanical processes are reversible.) This can
be done for a general deformation, thus obtaining the general constitutive equation
for the stress of an ideal rubber. For the sake of simplicity, we only show here
the procedure for a particularly simple deformation, uniaxial elongation. Con-
cretely, we may think of a cylindrical specimen of rubber being uniformly stretched
in the axial direction under the action of a force F.
Let us assume the principal stretch ratio along the axial direction is a.
Because of symmetry, the other two principal ratios are equal and, in view of
equation (12.3.5), are given by 1/.ja. Thus for the case considered equation
(12.3.9) becomes
(12.3.12)
332 Quantity F I So is usually called the engineering stress. The true stress (T is
the ratio F I S, with S the area of the current cross section. Since Sol S = a, the
Chapter Twelve
stress is given by
(T = 3ckTe (12.3.14)
Therefore, the Young modulus of the ideal rubber is 3ckT. Consequently, if the
rubber is incompressible, i.e., if it has a Poisson ratio 0.5, the shear modulus G
is given by
G= ckT (12.3.15)
(Tl2 = Gy (12.3.16)
(12.3.18)
An area where molecular modeling of polymers has been, and still is,
particularly active is the prediction of transport properties in the liquid state,
such as the diffusion coefficient or the viscosity. To avoid possible misunderstand-
ings, it is better to specify from the beginning that molecular modeling does not
predict values of either the diffusivity or the viscosity, but rather their dependence
on the molecular weight of the chain, just as the random walk analysis in Section
12.2 predicts the M dependence of the molecular size, not its value, the latter
depending also on the Kuhn length b, which is determined by the chemical details
of the chain. Similarly, in dealing with transport properties, one makes use of
an additional chemistry-dependent parameter, i.e., the friction coefficient of a
chain segment, the purpose of the theory being that of predicting how this "local"
transport property scales up to the level of the whole chain or of a collection of
them.
On the other hand, the scope of the theory is also more ambitious than
sketched above. In fact, momentum transfer in polymeric liquids is a much more
complex phenomenon than in ordinary liquids. While for the latter viscosity is
all one needs to know, polymeric liquids are non-Newtonian and viscoelastic
(or, in other words, they exhibit relaxation phenomena on a time scale which is
by no means negligibly small as compared to experimental time scales). Thus,
the purpose of the theory is actually that of predicting a constitutive equation for
the transport of momentum, i.e., for the stress. There is no room in this chapter
for such a scope, to which whole books are dedicated. It may be useful, however,
to gain some insight on how the problem is tackled, at least at an elementary
level. We note further that the concept of viscosity remains meaningful also for
polymeric materials because it can be shown that, for sufficiently slow flows,
their complex behavior approaches that of a Newtonian, purely viscous liquid.
(Of course, the same is true for the Maxwellian gas, only in the case of the latter
334 a flow of any pragmatic interest is almost invariably "sufficiently slow." In the
Chapter Twelve case of polymeric liquids, on the other hand, deviations from Newtonian behavior
take place well within conditions of practical interest.) All values of viscosity
reported subsequently refer to slow flow conditions only.
We shall first consider the case of extremely dilute solutions, where each
polymer chain may be thought of as being in contact only with the solvent.
Subsequently, we shall briefly touch upon the case of concentrated solutions and
polymer melts. In either case, the first property to be examined is the diffusivity.
Let us start by defining the friction coefficient of a molecule, &, and by
showing its universal relationship to the diffusivity D. Assume that a molecule
of a fluid is acted upon by a force F. That molecule will then move, relative to
the others, with a mean velocity v. The friction coefficient is defined as the ratio
(1:ZA.l)
cFj&-Dac/ax=o (12.4.2)
(1:ZAA)
C=M; (llA.5)
The other case is the opposite extreme. It assumes that the sphere containing
the polymer molecule is dynamically impermeable to the solvent, i.e., the polymer
segments close to its external surface "shield" the more internal ones, which thus
exert no friction. Since the polymer molecule now behaves as a solid sphere of
radius (r2)1/2, by considering Stokes's law for a sphere one writes
(ll.4.6)
where the two indicated proportionalities make use of either equation (12.2.2)
or (12.2.3) and are therefore valid for a 8 solvent or for a good one, respectively.
As one might expect, reality falls somewhere in between the two extreme
cases treated above. On the other hand, a more precise calculation would require
,accounting explicitly for the hydrodynamic interactions between polymer seg-
ments, i.e., solving for the flow field inside the sphere. We omit these complications
here and move on to consider the next property, i.e., the viscosity. More precisely,
we want to estimate the increase of viscosity over that of the solvent due to
addition of a polymeric solute.
A simple way of obtaining a prediction makes use of a result, again due to
Einstein, which holds for a dilute suspension of solid spheres. Einstein's result is
where ILs and IL are the viscosities of the solvent and of the suspension, respec-
tively, and e/> is the volume fraction occupied by the spheres. By assimilating the
polymer molecules to spheres with radius (r2)1/2, one obtains
(ll.4.8)
where c is the number of polymer molecules per unit volume and, again, the
exponent of M depends on whether we consider a 8 solvent or a good one.
Postponing a discussion of this result, we now consider a more general
approach. Indeed, the use of Einstein's formula for solid spheres neglects a
feature of the polymer molecules which we envisage might play some role, i.e.,
that they are deformable objects. The effect of a velocity gradient, by dragging
different parts of the same polymer molecule in different directions (relative to
the molecule center), is in fact "deformational." Moreover, the rigid-sphere model
is, as we have seen, an extreme case of friction behavior, and we would like to
explore the free draining extreme as well or, possibly, something in between.
336
Chapter Twelve
FIGURE 12.4.1. The elastic
dumbbell model, which may be
used to roughly simulate the
dynamic response of a polymer
in dilute solutions.
This equation states that if, at a given value of r, W is changing in time, the
change must be due to the fact that the flux J of dumbbells toward that value of
r is different from the flux of the dumbbells leaving the same value, the difference
being measured by the flux divergence (in r space).
In equation (12.4.9), J is the overall flux. It is readily recognized that J is
made up of three contributions, i.e.,
(12.4.10)
where J v is the flux due to the velocity gradient, J E that due to the spring elasticity,
and J o that due to diffusion.
The explicit expressions for these fluxes are not given here because we are
only interested in stating the problem in general terms. Suffice it to say that, once
the expressions for the three fluxes are substituted into equation (12.4.9), there
results a differential equation for W(r, t) which admits explicit solutions for
* More explicitly, if X, y, z are the Cartesian components ofr, W(x,y, z, t) dx dy dz gives the fractional
population at time t of dumbbells with components between x and x + dx, y and y + dy, z and z + dz.
338 arbitrary velocity gradients (as long as the spring elasticity is linear). Thus, the
Chapter Twelve
anisotropy induced by any flow can be evaluated, and the next question immedi-
ately poses itself. How do we obtain values of, say, the stresses induced by the
flow from this information?
The answer to this question or to similar ones (for instance, one might want
to get information about the optical anisotropy, Le., the birefringence) is as
follows. Macroscopically observable quantities, like a stress or a birefringence,
can be expressed as appropriate averages of some functions of the end-to-end
vector r. Thus, since the distribution of r is known, these averages are easily
calculated.
For example, the average which is required to calculate the extra stress a
(Le., the stress to within an arbitrary additive isotropic tensor, which is all that
the constitutive equation delivers for an incompressible fluid) is that over the
dyadic product rr. Specifically .
a = cH(rr) (11.4.11)
where H is the spring constant and c the number of dumbbells (Le., of polymer
molecules) per unit volume.· Equation (12.4.11) is obtained from the definition
of stress, Le., by ideally cutting through the material with a plane surface, counting
how many dumbbells are cut per unit area, and summing over the elastic forces
in those dumbbells. Of course, equation (12.4.11) only gives the stress contributed
by the polymer molecules, which adds to that due directly to the solvent. Unless
the solution is extremely diluted, however, the polymer contribution turns out
to be the dominant one.
An important comment on the structure of equation (12.4.9) follows. Since
the equation is first-order differential in time, integration from time zero up to
the current time requires an initial condition (Le., the initial distribution needs
to be known), as well as knowledge of the velocity gradient throughout the time
interval from 0 to t. In other words, W(r, t) depends on the previous history of
the velocity gradient (see Chapter 5), not just on its value at time t, i.e., the
material has memory for past kinematics. In view of equation (12.4.11), this
property of the distribution function is transferred to the stress, Le., the material
is viscoelastic. A loose analogy with the discussion in Chapter 5 can be obtained
by regarding the distribution function W(r, t) as the internal state variable;
equation (12.4.9) is then recognized as the kinetic constitutive equation for the
rate of change of the internal state variable. The analogy is not as loose as it
appears at first sight: the stress (a generalization of pressure) depends on the
internal state variable, and the value of the latter cannot be imposed externally
(like the velocity gradient) but is determined by its initial value and its intrinsic
kinetics of evolution in time. Finally, the property of fading memory discussed
* For those not familiar with tensor notation and r space averages, the meaning of equation (12.4.11)
is as follows. Assume one wishes to calculate, say, the xy component of a. Then, by calling X, y
and z the components of r, one has
T = ~/2H (12.4.12)
and
/-I: = ckTU2H (12.4.13)
which have the meaning of a relaxation time and a shear viscosity, respectively.
They will be discussed separately.
By using the expression for the spring constant H given by equation (12.3.3),
we first rewrite equation (12.4.13) in the form
(12.4.14)
where IL - ILs has been written instead of IL' since equation (12.4.13) only gives
the polymer contribution to the viscosity. Also, (r2) has been introduced instead
of nb 2 for a more direct comparison with equation (12.4.8). It is understood that
(r2) is an equilibrium average.
Again, two extreme cases can be considered. In one of them, by assuming
that the macromolecule is dynamically impermeable to the solvent, the friction
340 coefficient is taken to be proportional to (r2)1/2. Since it is also proportional to
the solvent viscosity, equation (12.4.8) is obtained again. At the opposite extreme,
Chapter Twelve
i.e., in the free draining case, , is proportional to M, and equation (12.4.13)
becomes
(12.4.15)
to relax back to equilibrium. More precisely, the dumbbell model predicts that,
after a flow or a deformation has been stopped, the stress (or any other measure
of the anisotropy induced by the motion) decays exponentially, with a time
constant T as given by equation (12.4.12). More detailed theories, like the
Rouse-Zimm model, predict a sum of exponentials instead of a single one, i.e.,
a set of relaxation times. The largest of them, however, is what really matters in
most cases, and it essentially coincides with that predicted by the dumbbell model.
The relaxation time depends more strongly on molecular weight than the
intrinsic viscosity. Again depending on hydrodynamic interactions and solvent
quality, the predictions vary somewhat, but roughly one finds
(12.4.16)
Thus, if M is large enough, T may well approach values of the order of, say,
seconds, the more so the more viscous is the solvent. This has important con-
sequences on the "deformation" of the polymer molecules. Indeed, as we have
already mentioned, a flow has a tendency to deform the molecular coils which, 341
however, is counteracted by Brownian motion tending to reestablish equilibrium. Polymers
The strength of the flow is measured by the magnitude r of the velocity gradient,
while the rate by which equilibrium is approached is measured by T. Thus, which
of the opposing effects will prevail is determined by comparing r with 1/ T. In
particular, if we have
r» l/T (12.4.17)
we may expect that the flow is effective in stretching and aligning the polymer
molecules. In some cases, these effects may have important practical con-
sequences.
We now move on to briefly consider the case where the polymer molecules
are concentrated. We may as well jump to the other extreme of a polymer melt,
the case of concentrated solutions not differing in essence from that situation.
Indeed, the essential difference in the dynamics between the dilute and the
concentrated case is the following. While in a dilute solution the interaction
between any polymer molecule and the surrounding medium, i.e., the solvent, is
purely frictional, in a melt each polymer molecule must also take account of the
fact that, when moving about, it cannot cut across the other chains. In other
words, the interaction is not merely frictional but, in some sense, topological.
To go directly to an extreme case, let us examine a melt of very long chains.
Each chain is still a random coil, i.e., it is an extremely convoluted object which,
on the whole, occupies a spherical volume the size of which is determined by
equation (12.2.2). This sphere, however, is not filled up by that single molecule
which actually only takes up a small portion of the available space. The rest,
which in the dilute case was occupied by the solvent, is now occupied by segments
of other long chains. We have therefore an extremely intertwined situation and
the molecules are said to be entangled.
We consider now the dynamics of that chain. By thermal motion, the chain
attempts to move about but, in so doing, it bumps repeatedly against impassable
topological obstacles constituted by the surrounding chains. At first sight, it might
seem that the diffusivity is zero, i.e., that the system is solid-like. Closer inspection,
however, reveals that the chain has retained the possibility of diffusion in spite
of the obstacles, but the price to be paid has increased enormously.
To see this possibility we refer to Figure 12.4.3, which gives a two-dimensional
picture of the situation. The chain is shown together with a number of dots,
which are meant to represent cross sections of surrounding chains with the plane
of the figure. The dots are impassable obstacles and therefore the chain is restricted
in its sideway motion to a space which, in three dimensions, looks like a tube
(the shaded region in Figure 12.4.3). On the other hand, the obstacles do not
prohibit the chain moving along its own length or, to be more precise, along the
length of this tube of lateral constraints. This particular kind of diffusion of
polymer chains in entangled systems has been called reptation, or snake-like
motion.
Let us now estimate the diffusion coefficient under these conditions. We
must distinguish between a diffusion process along the tube, regulated by a
diffusivity D, and the diffusion in space of the center of mass of the polymer
342 molecule, D M , which is observed macroscopically in diffusion experiments of
labeled chains.
Chapter Twelve
As far as the snake-like motion along the tube is concerned, it can be argued
that the polymer molecule only experiences an ordinary friction, regulated by a
friction coefficient C, D and C being linked by equation (12.4.4). We can also
envisage C strictly proportional to the length of the chain (there are no hydro-
dynamic interactions to account for in this case), and therefore
D= 11M (12.4.18)
L= Na; (12.4.19)
In fact the tube itself is a random walk of step length a and, of course, the
end-to-end square distance of the tube must be the same as that of the chain.
(12.4.20)
(12.4.21)
(12.4.22)
(12.4.20')
The prediction that the relaxation time grows with the third power of M in
a concentrated system, as compared to about the second power of the dilute case,
is also in reasonably good agreement with experiments. Actually, the experimental
results indicate a power slightly larger than 3, and a debate is ongoing about the
source of this minor difference.
344 Building upon the idea of reptation, which was first proposed by De Gennes,
Doi and Edwards have constructed a complete dynamical theory which leads to
Chapter Twelve
a constitutive equation for concentrated polymeric liquids. There is no room here
to discuss this theory. Suffice it to say that the chain is modeled as a Rouse chain
constrained in a tube, and the assumption is made that the tube segments, during
a motion, deform affinely with the continuum. At the same time, the chain attempts
to reestablish equilibrium by reptating out of the deforming tube, thus con-
tinuously generating at the extremities new, randomly oriented, tube segments.
A simple prediction of the theory is that, in slow flows, the viscosity scales with
M in the same way as the relaxation time, say
(12.4.23)
It is noteworthy that, for viscosity, the difference with respect to dilute solutions
is even stronger than that found for either the diffusivity or the relaxation time.
In fact, since p. in· a polymer melt is directly an intrinsic property (the melt
density is essentially independent of molecular weight), equation (12.4.23) is to
be compared with equation (12.4.15'), i.e., switching from the dilute to the
concentrated case implies a change from first- to third-power dependence on
molecular weight. Experiments essentially confirm this prediction, showing a
power slightly larger than 3 in concentrated systems.
It remains to discuss what happens in a polymer melt if the molecular weight
is progressively decreased. Obviously there must be a transition at some value
of M because, in the limit, the liquid even ceases to be polymeric. The transition
to a different kind of behavior is actually observed to occur at a critical molecular
weight Me which is still relatively large (order of thousands or tens of thousands,
depending on the polymer). Below the transition the behavior appears to be well
described by the Rouse theory or, roughly, by the dumbbell model. In other
words, the entanglements appear to have vanished.
The fact that Me is not too small is consistent with what was said before
about the relative magnitude between a and b. We should expect that there are
no entanglements if the end-to-end distance of the chains drops to values of
order a. The measured value of Me and the independent estimate of the value
of a are indeed mutually consistent. We note therefore that the entangled situation
is not obtained for all cases when polymers are concentrated; it is also required
that their molecular weight be large enough. If M < Me, a friction coefficient is
all that is needed to describe the dynamics, just as in the case of dilute solutions.
Finally, it is worth mentioning that the value of Me in concentrated solutions
increases with decreasing polymer concentration, as might be expected.
12.S. MIXTURES
(U.S.I)
where nl and n2 are the number of moles of the two components of the mixture
and Yt and Y2 the corresponding mole fractions.
Before examining this question, we must specify the state of the pure
components with respect to which SMIX is defined. Indeed, in dissolving a solid
polymer to form the solution, if the state of the pure polymer is, at least, partially,
crystalline, there is a positive entropy contribution due to phase change, which
it is appropriate to distinguish from that due to mixing in a strict sense.
The main part of the entropy change, which occurs when a polymer melts,
i.e., when it goes from the crystalline, ordered state to the amorphous state of
the liquid, is conformational. It has to do with the fact, discussed in the previous
sections, that many conformations are available to a chain in the amorphous
state, while a single one will exist in the crystal (excluding defects of the crystal
structure). It is readily estimated that the entropy change for a chain comprising
n segments is of order kn. We may use, for example, equation (12.3.1) giving the
entropy of a chain for which the end-to-end vector is assigned.
If it is assumed that, in the crystal, the conformation of the chains is the
fully extended one, for which r = nb, then equation (12.3.1) gives
In the amorphous state, we can use equation (12.3.1) with the average value
of r2. Thus, since (r2) = nb 2, we get
The meaningful quantity is the difference between the two, i.e., the entropy
change due to disorientation. Since n is a large number, we obtain
Of course, equation (12.5.4) should not be taken literally for at least two
reasons. It is based on the random walk chain model and, furthermore, we have
used equation (12.3.1) with r = nb, i.e., beyond its range of validity. The result
is correct, however, in an order-of-magnitude sense. A similar result was obtained
long ago by Flory with the aid of the lattice model. Another calculation, referring
to the aliphatic chain, is given as an example at the end of the chapter. All of
these calculations predict a disorientation entropy which, as anticipated above,
is of order kn per chain, i.e., of order k per chain segment. Thus, although the
entropy of melting is large on a chain basis, reflecting the large increase in internal
degrees of freedom in the liquid state, it is of a comparable magnitude to that
of small molecules when referred to a chain segment or "monomer." This is
346 reflected in the fact that the melting point of polymers shows no unusual behavior,
the enthalpy of melting also being proportional to n, when referred to a chain
Chapter Twelve
made up of n monomers.
We now proceed to estimate the entropy of mixing in the proper sense. It
is understood that the disorientation entropy is omitted and that we take a
standard state for the pure polymer which is already amorphous, such as a
polymer melt (a possibly imaginary state at the temperature of interest).
Following Hildebrand, a simple way of dealing with the entropy of mixing
is to use the concept of free volume which, by definition, is the volume available
to the center of mass of any molecule in the system, properly accounting for the
volume occupied by all other molecules. Thus, the increase in entropy which
takes place upon mixing results from the fact that the molecules of each species
will, in the mixture, also enjoy the free volume made available to them by all
other species.
Let us first consider the case of ideal gases for which the free volume coincides
with total volume since, by definition (if one interprets ideal gases as being
Maxwellian gases), the molecules are volumeless mass points. When, at constant
temperature and pressure, we form a mixture of gases, each one of them expands
from the original volume to that of the mixture. Thus, in the case of only two
species, the change of entropy is given by
(12.5.5)
where V. and V2 are the original volumes of the pure gases, V = V. + V2 being
the mixture volume. Now, since in an ideal gas the volume fraction coincides
with the mole fraction, equation (12.5.5) is the same as equation (12.5.1), i.e.,
ideal gases obey the ideal mixing law.
Equation (12.5.5) is more general, however, as long as V, V., and V2 are
interpreted as free volumes. It can be applied to liquids as well, polymeric or
otherwise. The problem, of course, becomes that of estimating the free volume,
by no means an easy matter in the general case.
To proceed with the calculation. and, what is more important, in order to
show the essential peculiarities resulting from the polymeric nature of at least
one of the components of the mixture, we make the simplifying assumption that,
in the liquid state, all species have the same free volume fraction at any given
temperature and pressure. In other words, we assume that the larger the volume
occupied by a molecule, the larger the accompanying free volume, so that the
ratio of the two is constant. We further extend this assumption to mixtures, i.e.,
the free volume fraction in the mixture is the same as that in the pure components.
This extension is, of course, equivalent to the assumption of volume additivity
upon mixing (V M1X = 0).
With the assumptions stated above, free volume is proportional to volume
and equation (12.5.5) becomes
(12.5.6)
where quantities cf>J are the volume fractions of the two components in the mixture.
Needless to say, equation (12.5.6) coincides with equation (12.5.1) if the
molar volumes of the two species are equal (as for ideal gases). This may well
be the case for a liquid mixture of small molecules, at least in some instances, 347
and at least approximately more often. Conversely, when one component is Polymers
polymeric and the other is not, the difference between the two equations is very
significant. We will subsequently call "solvent" the low molecular weight com-
ponent, over the whole concentration range.
We note that, although equation (12.5.6) is based on a somewhat arbitrary
approximation, it is nevertheless expected to portray the essential features of
polymeric behavior, i.e., to be much closer to reality, than equation (12.5.1) could
ever be. In fact, in order to obtain equation (12.5.1) from equation (12.5.5) also
in the polymeric case, we would need to assume that a molecule of polymer, in
spite of its enormous size, carries with it the same absolute amount of free volume
as does a small molecule of solvent. This would clearly be an absurdity. The
assumption that the relative amount remains unchanged is obviously much better,
though corrections may be required.
Postponing further discussion of equation (12.5.6), we proceed to consider
also the heat of mixing so as to reach an expression for the free enthalpy of
mixing. Following Flory, the enthalpy change which occurs when mixing a
polymer (subscript 2) with a solvent (subscript 1) can be expressed in the form
(12.5.7)
(12.5.8)
and (12.5.9)
Finally, by setting CPI = cP (the volume fraction of the low molecular weight
component), CP2 = 1 - cP, and one obtains
(12.5.11)
(12.5.12)
This equation sets an upper limit to the energy parameter X for achieving
complete miscibility. Now if X is, say, equal to I, i.e., if the solute molecule is
as small as the solvent molecule, this upper limit is X = 2. Conversely, if the
solute is polymeric, X » I, and the upper limit becomes essentially X = !. This
fourfold decrease in the maximum allowable value of X makes it much more
difficult to find solvents for polymeric substances. Note how the effect is purely
entropic; it is brought about by the large size of polymer molecules.
The situation is much worse if both components of the mixture are polymers.
In such a case, the entropic term is almost negligible and even a very small
positive contribution from the energy term makes the polymers immiscible. To
see this clearly, we need to reformulate somewhat the energy term. Since now
both components are polymeric, we redefine X on the basis of a polymer segment
of the size of a monomer, which is the correct equivalent of a solvent molecule.
Thus, if the molecules of polymer 1 are made up of Y monomers, equation
(12.5.8) essentially becomes
(12.5.13)
The latter equation already tells the whole story. Since Y is a very large
number, unless X is very small the last term will predominate over the entropic
contribution. More formally, if we now call X the number of monomers per
molecule of polymer 2 and assume for simplicity that the monomers of the two
polymers have equal volumes, we get the symmetric formula
and
(12.5.15)
the latter showing that, since both X and Y are large numbers, miscibility requires
that X be essentially zero (or, of course, negative).
Returning to the solvent-polymer case, it should be stressed that equation
(12.5.8) does not generally apply to extremely dilute solutions. In fact, the
derivation of the Flory-Huggins equation is based on the tacit assumption that
concentration is homogeneous, an assumption which breaks down in dilute
solutions. When there are very few polymer molecules in the solution, there will
be regions of pure solvent as well as regions, roughly spherical in shape, where
isolated polymer molecules will be present and where the local solvent concentra-
tion is smaller than the average. The Flory-Huggins equation starts to be valid
when the polymer concentration has reached the point where the chains overlap 349
extensively, so that everywhere the local concentrations of polymeric segments
Polymers
and of solvent are uniform.
We can readily estimate the critical concentration at which the chains will
begin to overlap. By taking the end-to-end distance as a measure of the coil size
we obtain, from either equation (12.2.2) or (12.2.3),
(12.5.16)
where c* is the number of polymer molecules per unit volume of solution when
the spherical domains come into contact. As previously, the reported powers of
M refer to the case of a (J solvent or to a good one, respectively. In terms of
volume, or weight fraction, the dependence on M obviously becomes
(12.5.17)
which shows that the larger the molecular weight, the sooner a polymeric solution
ceases to be dilute. In most cases a concentration of the order of 1% by weight
is already sufficient.
In the range of dilute solutions, the thermodynamic calculations become
more involved. Indeed, it is required to estimate both the entropic and the
energetic contributions as a function of the mutual distance of the chains, i.e.,
for different degrees of overlapping. First considering a system of only two chains,
it is found that free enthalpy generally decreases with increasing distance, i.e.,
the chains repel one another. From this result, one calculates the excluded volume
which can be attributed to each chain, and therewith the thermodynamic proper-
ties of the solution. The result holds up to second order in the concentration,
since only binary interactions were considered. Multiple interactions must be
accounted for to extend the results to higher order in concentration. Leaving
aside this complex matter, we only consider the special case where, in the binary
interactions, the entropic and energetic terms exactly match so that the excluded
volume vanishes. This is the situation in a (J solvent where the chains, while
repelling each other for entropic reasons, also attract each other because energy
favors polymer-polymer contacts better than polymer-solvent contacts and the
two opposing effects cancel out.
In such a case, since the polymer coils can interpenetrate freely, the whole
free volume of the mixture is available to the center of mass of each molecule,
without exclusions. Now, remembering that uniform availability of the free
volume is the hypothesis required for the Aory-Huggins equation to hold (quite
apart from other "minor" assumptions), it is concluded that equation (12.5.8)
also holds for a dilute solution in a (J solvent, up to quadratic terms in the polymer
concentration.
Rather than work with equation 12.5.8 (itself), it is better to first calculate
the chemical potential ILl of the solvent, which is obtained from equation (12.5.8)
by taking the baric derivative with respect to {II' With cf>1 and cf>2 given by equation
(12.5.9), one obtains
(12.5.18)
350 which shows that the 8 solvent corresponds to X = !, for which value the effects
of the binary interactions, represented by the quadratic term, vanish.
Chapter Twelve
Although equation (12.5.18) does not hold in general, its first-order term,
being independent of polymer-polymer interactions of any order, is of general
validity. Indeed, the first-order term corresponds to the classical first-order theory
of dilute solutions and expresses the colligative properties in the classical sense;
see Section 8.8. To within first order for the solvent, the Aory-Huggins equation
is in agreement with the classical colligative theory. Using only the first term of
equation (12.5.18), little algebra is needed to obtain the classical result for the
osmotic pressure:
where c' is the molar concentration of polymer. However, it should be taken into
account that, in a dilute polymer solution (dilute on a weight percent basis), the
molar concentration of polymer is very low and hence colligative properties such
as the boiling-point change are very small; osmotic pressure is, however, still
quite within measurable ranges, since it is very large for ordinary low molecular
weight solutes. Furthermore, membranes which are truly semipermeable do exist
in the case of polymers, which are easily rejected for steric reasons because of
their large molecular size. Thus equation (12.5.19) may be used to determine the
(number average) molecular weight of polymers.
Returning now to more concentrated solutions, it may be interesting to
calculate the solvent activity, which is of importance in vapor-liquid equilibria
of solutions, devolatilization of polymer melts, etc. By definition, the left-hand
side of equation (12.5.18) coincides with the logarithm of the solvent activity at.
Therefore, by using the full expression on the right hand side and by neglecting
11X with respect to 1, we obtain
(12.5.20)
This equation shows that the activity never coincides with the volume fraction,
not even when X = 0, as might perhaps have been surmised from a superficial
comparison of equations (12.5.6) and (12.5.1), i.e., by presuming that the solvent
volume fraction plays in this case an analogous role to the mole fraction in ideal
solutions.
In the limit of q,2 approaching unity, i.e., for a polymer containing a very
small amount of solvent, equation (12.5.20) becomes
(12.5.21)
which shows that the modified Henry constant of the solvent (modified in the
sense that it is based on volume fraction rather than mole fraction) is given by
pS exp(1 + X), with pS the vapor pressure of the pure solvent. [This result could
be considered as stating that exp(1 + x) is the modified infinite-dilution activity
coefficient of the solvent.]
A final comment on the Flory-Huggins equation concerns the temperature 351
dependence of the energy parameter X. Since Polymers
S = -8G/8T (12.5.22)
then in order that equations (12.5.6) and (12.5.8) be consistent with each other,
one should find that X varies inversely with absolute temperature. Although
indeed X generally decreases with increasing temperature, an exact inverse propor-
tionality is a rare event. This implies that the last term in the Flory-Huggins
equation, describing the polymer-solvent interactions, also cont.ains entropic, not
merely energetic, contributions. In other words, by maintaining the form of the
Flory-Huggins equation, equation (12.5.6) should assume the form
(12.5.23)
For this reason, it is preferable to refer to X with the more generic name of
interaction parameter rather than energy parameter, though there is no doubt
that the greatest part of the interaction term comes from energetic contributions.
It is perhaps appropriate to recall again that the Flory-Huggins equation is
obviously an approximation, based as it is on the assumption of constant free
volume fraction throughout the range of concentrations. It is also a very simple
equation, however, which is unquestionably convenient for quick, yet reasonably
accurate estimates. Refinements, obviously at the expense of simplicity, have
been, and still are being worked out, especially for the case of polymer blends
where, as previously shown, fine details may become crucial in deciding about
the miscibility (or compatibility) of the two polymers.
So far, we have only examined the thermodynamics of mixtures in which
the polymer molecules are not stretched. This is not the only possibility, however.
A classical example where stretched chains coexist with a solvent is that of swollen
rubbers. Let us consider a polymer and an ordinary liquid which are miscible in
all proportions, so that the polymer will readily dissolve in the liquid. If we now
first cross-link the polymer to form a network and then insert the resulting piece
of rubber into the liquid (or expose it to its vapor), since the cross-linking
operation has not significantly changed the "chemistry" of the polymer, there
remains a tendency to mix which, in view of the obvious impossibility for the
rubber to go into solution, will result in the fact that the solvent penetrates the
network, swelling it up to some larger volume. In the swelling process the chains
get stretched. It is this progressive stretching that will eventually stop the swelling
process. The problem then becomes one of determining the equilibrium volume
ratio between the swollen and dry rubber.
To this end, we write the free enthalpy change which occurs upon swelling
as the sum of a mixing and an elastic contribution:
(12.5.24)
The mixing term is given by the Flory-Huggins equation which, in view of the
fact that the rubber network is a single giant macromolecule, is here rewritten
without the n2 term:
(12.5.25)
352 For the elastic contribution, we can use equation (12.3.9) of tre section on
rubber elasticity where, since the swelling process is an isotropic expansion, we
Chapter Twelve
can put
(12.5.26)
(125.27)
We are now ready to calculate the chemical potential of the solvent in the
swollen rubber. By regarding a as related to the polymer volume fraction in the
swollen polymer, q,2, namely
(12.5.28)
(125.29)
where X is now the ratio of the molar volumes of the network chain and solvent,
baric differentiation with respect to nl yields
It should be noted that, as long as X :5 !. i.e., for a solvent which mixes with the
parent polymer in all proportions, this equation would never be satisfied without
the elastic term; more precisely, it would be satisfied with q,2 = 0, i.e., for an
infinitely large swelling ratio. Conversely, with the elastic term included, a solution
is always found with 4>2 in the interval 0 < 4>2 < 1, which defines the equilibrium 353
swelling ratio £1'*. If £1'< £1'*, further solvent wants to penetrate the rubber. On Polymers
the other hand, if a> £1'*, the solvent is squeezed out as a result of rubber
elasticity. Similar considerations apply to the case of exposure to a nonsaturated
vapor, i.e., if the activity of the solvent is less than unity.
Although qualitatively the situation is as just described, quantitatively the
above equations should not be taken too literally and, in fact, they do not compare
too favorably with data. Now, quite apart from the minor imperfections of the
Flory-Huggins equation, which were discussed previously, there are major uncer-
tainties about the elastic term, and even about the additivity assumption embodied
in equation (12.5.24). It should be remembered that the rubber elasticity theory,
as presented here, refers to a highly idealized situation. To mention just one
source of possible deviations, we note that, when the polymer is cross-linked by
some chemical means, many entanglements that the chains formed get trapped
in the network. These topological constraints add further connectivity to the
network, which is ignored in the classical theory. The theory refers to a network
of so-called phantom chains, which can cross each other freely. Although there
have been many attempts to account for entanglements in rubber elasticity, there
is no general consensus as to the appropriate way of dealing with this problem.
As far as the additivity assumption is concerned, namely equation (12.5.24), there
have been speCUlations that the solvent does not behave in exactly the same way
when mixing with a relaxed polymer, as in an ordinary solution, or with stretched
chains, as in a swollen network. In the latter case, owing to local anisotropy
existing in the neighborhood of a stretched chain, the solvent close to the chain
would be induced by a polarization effect to orient somewhat, thus changing the
entropy as well as the interaction with the polymer.
Whatever the present limitations of the theory, the fact remains that, when
dealing with polymeric substances, one frequently encounters practical situations
where the molecules are stretched. Suffice it to mention processes where a
polymeric solution or a melt is subjected to a flow or deformation. The thermo-
dynamic effects arising from chain stretching can be significant. There exists
accumulating evidence showing that the polymer-solvent and polymer-polymer
compatibilities (or miscibilities) are changed during a flow process. Effects due
to chain stretching are also important in crystallization processes, to the point
that crystallization will take place at a temperature at which the relaxed chain
would not crystallize (see also Section 5.4). This effect had long been known for
certain rubbers, and was subsequently demonstrated for flowing polymers, both
in solution and in the melt.
The rationale for a change in crystallization temperature brought about by
chain stretching is readily found. We recall that the equilibrium temperature at
which a phase change occurs satisfies the equation
T* = DR/DS (12.5.32)
where DR and DS are the jumps of enthalpy and entropy across the phase
change. For the liquid-solid transition of ordinary substances, since both phases
are rather insensitive to pressure, there is no easy way of changing T*. For the
case of polymers, however, we enjoy an extra degree of freedom, Le., we can
354 stretch the molecules in the liquid (or rubbery) state. Both DH and DS will
Chapter Twelve
change in general but, prominently, there will be a change in DS upon stretching
the chains in the liquid. The change is in the direction of decreasing DS since
the stretched chains have less conformational entropy, i.e., they are in this respect
closer to the crystalline state. The transition temperature accordingly increases.
a
b
FIGURE 12.6.1. (a) The excluded volume in the binary interactions of rigid rods for a
parallel configuration. (b) The same quantity for a perpendicular arrangement.
356 it is of the same order of magnitude as the particle volume. Conversely, if the
Chapter Twelve
two rods are perpendicular to each other (see Figure 12.6.1b), the excluded
volume becomes of the order of d1 2 , i.e., much larger. If the aspect ratio 1/ d is
a very large number, the "parallel" excluded volume can be neglected with respect
to the "perpendicular" excluded volume. Then, by calling 0 the angle formed
by the rod directions in binary interactions, one may write
(12.6.1)
where, as usual, the operator ( ) indicates an ensemble average which, this time,
is over the orientational distribution of the rod-like particles.
Now, if the number of particles per unit volume of suspension satisfies the
inequality
c« 1/ dl 2 (12.6.2)
then the collective excluded volume of the particles is much smaller than the
suspension volume even if (sin 0) is of order unity. As a result, both the positional
and orientational distributions of the rods will be random so as to maximize the
entropy.
Conversely, let us assume that c is increased to values of order 1/ df or
larger. Then, with a (sin 0) value of order unity, as pertains to an isotropic
orientational distribution, the excluded volume would fill up the entire available
space, i.e., the particles would lose the translational degree of freedom, and the
corresponding positional entropy would drop to negligible values. If, however,
the particles choose to orient so as to become almost parallel to each other, then
(sin 0) approaches zero and the translational degrees of freedom are restored. In
other words, in this range of concentrations two opposing effects come into play.
By decreasing (sin 0), the orientational contribution to entropy decreases but,
simultaneously, the positional contribution increases because of the correspond-
ing reduction in the excluded volume. A compromise will be found with an
appropriate anisotropic orientational distribution which maximizes the total
entropy.
The detailed calculations are somewhat involved and will not be reported
here. The results show the following behavior. By increasing the concentration,
the suspension remains isotropic up to a critical concentration c1 • If C1 < c < C2,
where C2 is a second critical concentration, two phases coexist, having concentra-
tions C1 and C2, respectively, the former isotropic and the latter liquid crystalline.
Finally, if c > C2, only the anisotropic phase exists, with a degree of orientational
order which progressively increases as c increases.
Both C1 and C2 are of order 1/ d1 2 • We note that, if the aspect ratio of the
rods is large, such a concentration level can be fairly low. In terms of volumetric
fraction, it becomes
(12.6.3)
i.e., it is well below the close packing limit, which is approached when cP becomes
of order unity. Thus, a theory based on binary interactions alone is a good
approximation, and it becomes exact in the limit of an infinite aspect ratio.
We note further the peculiar character of the equilibrium between the two 357
phases with concentrations C 1 and C2' Since no energetic contribution is involved, Polymers
not only is the chemical potential the same in the two phases, but also the partial
molar entropy Sf is continuous across the phase transition (the latent heat is
zero: in this sense, this is a secondary phase transition; see Section 4.5). The two
phases differ only in the way the same Sf is obtained. This is possible because
we now have an internal state variable, which is the degree of orientational order.
If we call p this orientational parameter, defined in such a way as to become
zero in the isotropic solution, and if S~ is given by a constitutive function s~( C, p),
the phase equilibrium condition is
(12.6.4)
where P2 is the value of the orientational parameter in the anisotropic phase and
J = 1,2 indicates the solvent and the rod-like solute.
Of course, in actual systems energetic effects will also be generally present
and become superimposed on the purely entropic effects just discussed. Energetic
interactions can also induce anisotropy on their own account. Thus, in many
cases, the liquid crystalline state is brought about by a combination of factors.
Small molecules which give rise to liquid crystalline phases (such as discussed
in Section 4.4) are typically elongated in shape, Le., they might crudely be
compared with rods having a small value of the aspect ratio. This geometrical
factor, which by itself might be insufficient to induce anisotropy, is enhanced by
coupling with some form of anisotropic polarizability that reinforces the tendency
of the molecules to align parallel to each other.
Returning to long rods, i.e., to the polymeric case, we now briefly examine
the effects of this shape on transport properties, namely, on diffusivity and
viscosity. The friction coefficient of a rod varies somewhat depending on whether
the rod moves parallel or perpendicular to its own axis. The difference is only
by a factor of 2, however, and, to within a logarithmic factor containing the
aspect ratio, the friction coefficient is proportional to rod length. Therefore, in
dilute solutions, the diffusivity is obtained as
(12.6.6)
The difference between the rigid dumbbell and the rod-like particle is only
in a logarithmic term containing the aspect ratio, which results from considering
the hydrodynamic interactions between the various segments of the rod. Thus,
equation (12.6.6) is essentially correct, i.e., the relaxation time of a dilute solution
of rod-like polymers scales with about the cube of molecular weight.
It can further be shown that the contribution to viscosity due to rod-like
polymers in dilute solutions is related to the relaxation time in the same way as
for the flexible ones, i.e., that [compare equations (12.4.12) and (12.4.13)]
where c is the number of rods per unit volume. It follows that, in the present
case, the intrinsic viscosity scales with M according to
(12.6.8)
It should be noted how the rigid polymers give rise to larger power exponents
than encountered in the flexible case.
The difference in the dynamics between the rigid and flexible polymers
becomes even more pronounced in the concentrated case. The rod-lii5e solution
becomes concentrated in a dynamical sense when there is a sizeable amount
of interparticle collisions such that the particle rotations become hindered.
Since the volume spanned by a rod in its rotational motion is of order the e,
hindrance to rotation will start to occur above a critical concentration of the
order of
This criterion does not involve the rod diameter d, but only its length. Since
1/ d ;> 1, c* is much below the concentration for the isotropy-anisotropy transition
discussed earlier.
(12.6.10)
If c » c*, then a« I. Within the tube, the rotations are constrained to small
angles of order a/ I, i.e., the rod is entangled in much the same way as for the
con.centrated flexible case.
In order to perform sizeable rotations, i.e., much larger than a/ I, the rod
must diffuse longitudinally. Each time it diffuses longitudinally by a distance ~
the orientation will change by an amount of order a/ I. Now, since the time
interval t to perform such a step is of order
(12.6.11)
(12.6.12)
Making use of equation (12.6.6) for the M dependence of D/12, and of equation
(12.6.10) for the value of a, equation (12.6.12) gives
(12.6.13)
(12.6.14)
(12.6.15)
where cp* = (d/I)2, while CPt and CP2 are both of order d/ L
If 0 < cP < cP *, the solution is dilute and, of course, isotropic. The relaxation
time and the viscosity increment scale approximately with M3 and c' M2, respec-
tively. If cp* < cP < CPt, the solution is concentrated but still isotropic. The relaxa-
tion time and the viscosity scale with C'2 M7 and C'3 M 6, respectively. In the small
range CPt < cP < CP2 two phases exist, one isotropic and the other liquid crystalline.
For cP > CP2, the solution is anisotropic and has a smaller viscosity and relaxation
time than the limiting isotropic solution at CPt. However, when the close packing
condition is approached, the polymer-polymer friction dominates over the poly-
mer-solvent friction and the viscosity will rise again. Indeed, there will eventually
be a transition to a solid state, be it glassy or crystalline. Finally, the inclusion
of energetic effects in the above picture may result in the fact that transition to 361
a solid state occurs much earlier, thus canceling some of the above regimes.
Polymers
Examples
1. We wish to obtain the result in equation (12.2.2) directly, i.e., without using the
distribution function. We refer to Figure 1.2.2 which shows the chain of Kuhn segments,
or random walk. If we indicate by bI the vectors corresponding to the chain segments,
the end-to-end vector is obviously obtained in the form
(12.E.l)
r2 = r •r = (I b I ) • (I bJ )
= nb 2 +I I bI • bJ (12.E.2)
where the last double sum is over J different from 1. When taking the ensemble average
of this equation, the last sum vanishes because, when I differs from J, there will be as
many positive terms as there are negative terms, and hence equation (12.2.2) is obtained.
3. We wish to find the disorientation entropy of the aliphatic chain by assigning equal
probabilities to trans and gauche conformers. Since to each next carbon atom in the chain
there are one trans and two gauche alternatives, the number of conformations is of order
3 n , where n is the number of carbon atoms along the chain. All of these conformations
have equal probability. Therefore
(12.E.6)
362 We wish to calculate the concentration dependence of the end-to-end distance in the
concentrated case.
Chapter Twelve The polymer volume fraction </>* at which the isolated chains will just "touch" each
other (nb 3 is taken as the volume occupied by the segments of the chain) is given by
(12.E.7)
By assuming power-law dependencies in the concentrated case as well, we write
(r2)CONC in the form
(12.E.8)
which is dimensionally correct, and automatically satisfies the crossover between the two
regimes. The unknown value of m is now found by imposing the condition that (r2)CONC
be proportional to n since, in the concentrated case, the excluded volume effects are
screened out at the scale of the chain dimensions. Thus, from the condition
6/5+4m/5=1 (12.E.9)
we get m = -1/4. The result is therefore
(r 2>CONC = nb2c/J -1/4 (l2.E.IO)
This result, first obtained by Daoud, is in good agreement with neutron scattering
experiments of deuterated chains in concentrated solutions.
Problems
12.1. Find the general relationship between F and r which replaces equation (12.3.3) for arbitrary
chain extensions. [Hint: The distribution of segment orientations in the chain subjected to force F
is the Boltzmannian C exp(Fb cos 6/ kT), where 6 is the angle formed by the segment with the
direction of the force and C is a normalization constant. Next calculate r as nb(cos 6).]
12.2. Find the stresses generated by deforming a rubber by a traction in direction 1 accompanied
by a contraction in direction 2, while in direction 3 the rubber dimension stays constant (planar
extension).
12.3. Explain the justification for using results which apply to free chains, such as the Gaussian
distribution of equation (12.2.1) [from which equations (12.3.2), and hence (12.3.9), are obtained],
to predict the behavior of deformed rubbers. In a deformed rubber, the chains are not free nor are
they randomly distributed.
12.4. By assuming that, in a concentrated solution of entangled polymers in good solvents, the
concentration dependence of the diameter of the tube of constraints is of the form a = </> -3/4, find
the concentration dependence of the relaxation time by further assuming that the friction coefficient
stays constant.
12.S. Find the limiting value of the interaction parameter for complete miscibility of two
polymers having X = Y = 100.
LITERATURE
THERMODYNAMICS OF
ELECTROMAGNETISM
R. E. ROSENSWEIG
Exxon Research and Engineering Company
Annandale. New Jersey
NOTATION
Subscripts
Total
Species i; also, internal
m Magnetic; also, per unit mass
e Electric; also, external
n Normal
1/ Viscous
v Per unit volume
o Value in absence of a field (except in 1-'0 and Eo)
Superscripts
* Modified
(over) Denotes partial quantity
o Reference value
Field averaged quantity
Denotes evaluation in the material frame of reference
Notes
(i) The mole is the amount of substance of a system which contains as many
elementary entities as there are atoms in 0.012 kilogram of carbon-12.
(ii) iYl denotes a closed region with a piecewise smooth boundary aiYl.
13.1. AN OVERVIEW
In the past chemical engineers have paid scant attention to the thermodynamics
of electromagnetic systems. With the advent of new processing concepts, novel
systems, and new materials including higher temperature superconductors, the
topic is assuming a greater importance. This treatment introduces the student or
graduate to the subject, building on fundamental principles in sequential
fashion with the goal of encompassing both physicochemical and transport
principles. A number of diverse but related topics are developed in a unified
fashion in comparison to the existing literature in the area which is incom-
plete, scattered, and often deficient. Certain of the topics developed are
important in current engineering practice and others represent areas for future
innovation.
Our treatment begins with a review of electromagnetic units and the statement
of Maxwell's equations, of which use will be made of every term at some point
along the way. However, most of the subject matter can be understood with
concepts of the uncoupled magnetostatic and electrostatic fields, and the corre-
spondence between these analogous systems is developed initially. Obtaining
correct expressions for electromagnetic work is of paramount concern. Because
of its importance this task is approached from several directions: via one-
dimensional systems wherein the physics is easily understood although the gener-
ality of results is uncertain; from the complete Maxwell's equations which yield
the generally accepted but limited result applicable to fixed volumes only; and
finally with a treatment based entirely on macroscopic classical concepts that
broadens the Maxwell result to apply for a substance that changes its mass
density in the process of becoming magnetically or electrically polarized. This
fundamental result is subsequently used in developing all the remaining topics
in the chapter. 369
370 The culminating topics include applications to problems of phase change,
chemical reaction, and other equilibrium processes as well as the formulation of
Chapter Thirteen
rate processes in dissipational systems of momentum and mass transport with
polarizable species.
B = #£o(H+M) (2.1)
The parameter #£0 is called the permeability of free space and has the value
#£0 = 411" X 10-7 H m-t, where H (not to be confused with the magnetic field)
stands for the henry. Other numerically equivalent units of #£0 are tesla-meter
per ampere (T m A-I), and newtons per square ampere (N A-2) or m kg S-2 A-2,
and m2r N- I • The quantity M denotes magnetization, a material property denot-
ing the state of magnetic polarization of magnetized matter. It can be seen from
equation (2.1) that only in the presence of magnetized matter does B differ from
#£oH.
Materials scientists frequently work in the cgs system of units in which
distance is measured in centimeters, mass in grams, time in seconds, and electric
current in amperes. In a vacuum in the cgs system and B field (in gauss) is
numerically equal to the H field (in oersteds) and B = H + 411"1 = H + M where
1 is the intensity of magnetization and M is known as the ferric induction. The
SI unit of magnetic induction, the tesla, is equal to 104 gauss.
The Earth's magnetic induction is about 7 x 10-5 T (0.7 gauss) in magnitude
with a horizontal component at the latitude of New York City of about 5 x 10-5 T;
the field of a ceramic· permanent magnet is typically 10-1 T, and an iron yoke
laboratory electromagnetic 2 T. Liquid-helium-cooled (4.2 K) superconducting
magnets made of metal alloys routinely produce magnetic induction of 5 T and
have been operated at 20 to 50 T. The limiting high temperature above which a
superconductor reverts to a normal conducting state was dramatically increased 371
in 1986 with the discovery of superconductivity in a class of rare earth copper
Thermodynamics of
oxide compositions for which J. G. Bednorz and K. A. Muller won the Nobel Electromagnetism
Prize in physics in 1987. Operation above the liquid nitrogen temperature (77.3 K)
has been demonstrated and there is general optimism for achieving higher
temperature operation, possibly above room temperature in suitably modified
materials. The cost of replacing liquid nitrogen coolant is less by a factor of
about 500 than liquid helium due to the 10 times larger volumetric heat capacity
and 50 times cheaper cost of the nitrogen.
Electrostatic fields are conveniently produced by applying a potential
~ifference to an electrode pair. Because electrodes can be configured as thin
conducting surfaces, they are often quite compact (think of the transparent
electrode in the liquid crystal alphanumeric display of a wristwatch). However,
the achievable energy density of magnetostatic fields exceeds that of electrostatic
fields as free magnetic charges (monopoles) are unknown and breakdown does
not occur as field intensity increases.
It will be recalled that the strength and direction of an electric field is
described at each point by a vector E such that the force acting on a small
stationary test charge q placed at this point is q E. The vector E is called the
electricfield. The conceptually analogous magnetic vector is H. Magnetized matter
behaves as a collection of an equal number of oppositely charged poles, Le., as
dipolar matter. Polarized dielectrics and ferroelectric materials provide the electric
dipolar analog. The electrically polarized media are characterized by the polariz-
ation vector P and a vector D, the displacement field, defined as
D=eoE+P (2.2)
Faraday's law
v x E = -aD/at (3.1.1)
VxH=Jr+aD/at (3.1.2)
V·D=Pr (3.1.3)
V·D=O (3.1.4)
Faraday's law relates the circuital voltage that appears when the flux linkages 373
vary with time, as in an electrical generator, or for that matter in an electromagnetic
Thermodynamics of
wave traveling through space; there need be no electrical current flow nor Electromagnetism
conductor present. Ampere's law relates the magnetic field that curls round a
current flux, corrected for unsteady values of electric field; wound magnetic field
sources rely on the former while the latter is important in wave propagation.
Gauss's law (I) tallies the field lines emanating from a distribution of charge,
and Gauss's law (II) reflects the circumstance that isolated magnetic poles are
unknown; a line of magnetic induction closes on itself.
Constitutive relations connect the fields D and H to the fields E and B. In
matter that is moving relative to the laboratory frame the field variables must be
evaluated in the frame of the moving matter. For quasi-stationary processes no
distinction need be made and one may write
D = D(E,p, T) (3.1.5)
and
H = H(B,p, T) (3.1.6)
where it is also assumed that the magnetic and dielectric parameters are uncoupled
from each other. The defining equations, discussed previously, are
D = EoE+P (3.1.7)
and
B = J.'o(H+M) (3.1.8)
P and J.'oM have physical significance as electric and magnetic dipolar density
in substances.
In equation (3.1.2) J r is the free current density. The term "free" distinguishes
such charge from the "bound charge" associated with the electric dipolar matter.
If there is more than one type of charge carrier, the net charge density Pr is equal
to the algebraic sum of all the charge densities, while the net current density'Jr
equals the vector sum of the current densities due to each carrier. Then, because
net charge is conserved, an equation of conservation can be written a priori as
(3.1.9)
[B· 0] = 0 (3.1.10)
374 and
Chapter Thirteen [H x nJ =0 (3.1.11)
V·D=O (3.2.3)
V·D=O (3.2.4)
D = EoE+P (3.2.5)
B = lLo(H+ M) (3.2.6)
Further, when the fields change slowly, as in a reversible process carried out at
an infinitesimal rate,
aD/at = 0 (3.2.7)
and
aD/at = 0 (3.2.8)
In this case the equations break into decoupled sets of magnetostatic and
electrostatic relationships having analogous forms.
Magnetostatic Electrostatic
(3.2.16)
(3.2.17) 375
Thermodynamics of
(3.2.18)
Electromagnetism
This correspondence between such magnetic and electric systems will spare the
necessity of separately discussing both topics in every possible instance.
As mentioned previously, electric field systems differ from magnetic systems
in that free charge exists in the former with no phenomenological analog in the
latter. To preserve the analogy space-charge effects must be eliminated in the
electric field systems. This can be accomplished if alternating electric field is
applied at a frequency w greater than the reciprocal dielectric relaxation time
CT / Ii of the polarizable substance (CT is the electrical conductivity).
The modern view coincides with Maxwell's-the energy resides in the field.
As convincing evidence, the electromagnetic energy constituting a light ray
continues to propagate after the source is extinguished.
This section develops expressions for the electromagnetic energy in simple
electric and magnetic field systems. The systems are chosen deliberately simple
to aid physical understanding. However, the results have a more general
significance as will be established.
D=eE (4.1.1)
which is the definition of e. In this simple geometry lEI = cp / I. Despite its name,
e is not usually a constant but depends on temperature, mass density, frequency,
and magnitude of the field. For so-called linear dielectrics Ii is independent of
E. Typical values of relative permittivity lir are listed in Table 13.2 for various
376
Chapter Thirteen
! Gauss, Surface / +q +
FIGURE 13.1. Two thin parallel·plate electrodes of area A at potential difference e. The
dashed line represents a Gaussian surface to derive the relationship between displacement
D and surface charge density ± q (the free charge).
e r ,= el eo (4.1.2)
The values cited in Table 13.2 pertain to a steady value of the applied electric
field E. Materials having a large relative permittivity are usually composed of
highly polar molecules. When the potential difference across the electrodes is
increased from e to e + de, a differential of electrical work dW. is performed on
the slab,
dW. = edq (4.1.3)
where Iql is the charge on a plate. Assuming a negligible effect of fringe fields
so that the charge is equally distributed over the surface area A of a plate, charge
is given by
q = uA (4.1.4)
where u is charge density, coulomb/m 2 • Thus, Gauss's law (I) can be integrated
over a volume with the shape of a small pillbox straddling the interface between
TABLE 13.2
The Relative Permittivity for Various Substances at Room Temperature
and Zero Frequency
Dielectric strength
Material er (kV'm- 1 )
Vacuum 1.00000 00
Air 1.00054 800
Teflon (polytetrafluorethylene) 2.1 60,000
Transformer oil 4.5 12,000
Pyrex glass 4.5 13,000
Ruby mica 5.4 160,000
Pure water 80
A ferroelectric titanate >2100 2000-12,000
the positively charged electrode and the dielectric substance, 377
LV, L
Thermodynamics of
Electromagnetism
D dV = Pr dV = uA (4.1.5)
r V. DdV = Ja9t
J~
rD' n dS = DA (4.1.6)
Thus, the displacement evaluated at the interface equals the surface density of
electric charge and q = DA. Because E = lEI = ell, equation (4.1.3) now becomes
1
-dW
V e =EdD (4.1.9)
where V = Al is the volume of the dielectric slab. Hence the work done on the
slab by the electrical circuit has been expressed as a volumetric density in terms
of electric field quantities evaluated within the dielectric substance. It should be
noted that the dielectric substance was tacitly assumed constant in volume in
this derivation, a restriction that is removed in Section 13.5.
Thermodynamics of a closed system at its roots is concerned with heat flow
or its absence. Because the conditions of heat flow during the charging process
have not yet been specified, the right-hand side of equation (4.1.9) lacks precise
meaning. To give the result a definite meaning the first law of thermodynamics
is applied to a unit volume of the dielectric slab,
(4.1.10)
where dQv is the differential of heat added to unit volume of the slab, dWy =
d (Wei V) = (dWe)1 V is the differential electric work done on unit volume of the
slab material, and U y is the internal energy of a unit volume of the slab. For a
reversible process dQy = TdSy, so from equations (4.1.10) and (4.1.9) we obtain
E dD = dUy - T dS y (4.1.11)
378 Supposing the process to be accomplished isothermally through efficient heat
exchange with the surroundings permits writing dUv - T dSv = d( U v - TSJ, so
Chapter Thirteen
that
(4.1.13)
d4> dB
e=n-=nA- (4.2.1)
dt dt
the first part of which can be deduced from integration of Faraday's law (3.1.1)
though not so simply if rigor is desired. The flux in the system is 4> = BA, where
A is the constant cross-sectional area of the sample and B is the uniform induction
field. Ampere's law (3.1.2) in the absence of displacement current integrates
Magnetizable Matter
Cross Section A
---- e·---
FIGURE 13.2. Sketch to develop expression for electrical work performed in magnetizing
a material.
readily as shown in standard texts to yield the relationship between magnetic 379
field magnitude H and current i,
Thermodynamics of
Electromagnetism
H = nill (4.2.2)
and substituting for e and i from the above and cancelling common factors gives
Similar to the electrical case, the work again has been expressed purely in terms
of field variables. Incorporating this work expression into the combined first and
second laws applied to a unit volume of the magnetizable material proceeds in
the analogous manner as for the electrical case and gives
E2 D2
A v.. = E2 - =2E- (E.4.1.1)
(EA.I.2)
380 Table 13.3 lists computed values of field energy density for various systems. All the energy
stored in fields is potentially available to perform work. Hydrocarbon fuel such as gasoline
Chapter Thirteen
has a heat of combustion of about 3.2 x 10 10 J/m 3 • Assuming a 30% thermal efficiency
for conversion of the energy to work in an internal combustion engine the available energy
density is 9.6 x 109 J/m 3 • Thus, the calculated energy storage in superconductors
approaches that of chemical fueL The difficulty of containing the energy is considered in
a later example.
Quantity J r was eliminated using Ampere's law (3.1.2), in the first term on the
right-hand side, and the second term is identically zero on account of Faraday's
law (3.1.1). By introducing the vector identity
V . (E x H) = E . (V x H) - H . (V x E) (4.3.3)
equation (4.3.2) can be rewritten as an integral expression giving the work done
on the system by the external sources in establishing the field:
hl~
......
"-
a cI'>.~
~'S
""'~" '~~." w
~. f'J 00
~..sa, ......
382 The volume integral in the last term is transformed to a surface integral using
the divergence theorem:
Chapter Thirteen
r V. (E x H) dV =!J.~ (E x H) . n dS
J~
(4.3.5)
Here E x H, called the Poynting vector, having units of watts per square meter,
is interpreted as the flux density of electromagnetic energy through a spatial or
material surface; only its integral over a closed surface has measurable sig-
nificance. On the assumption that Hand E go to zero on the system boundaries,
expression (4.3.4) becomes
W. =
•
i f, t(
~ 0
aD
E·-+H·-
at dtdV aB)
at (4.3.6)
The volume integrations are carried out over stationary volume elements, so
expression (4.3.6) can equivalently be written as
(4.3.7)
dWy = H dB + E dD (4.3.8)
in agreement with the results obtained in the uniform field systems and given as
equations (4.1.9) and (4.2.5).
Expression (4.3.8) requires further transformation to treat the thermo-
dynamics of mass having variable volume, a step accomplished in the next section.
where Qv is heat added per unit volume, p is the mass per unit volume, Uv is
internal energy per unit volume, and H dB is the expression for magnetic work
performed per unit volume, derived previously. It is noted that equation (5.1)
contains no term for work of expansion and this might at first appear an oversight.
However, for a system defined as the variable content of a constant volume in
space, the boundaries do not move and thus it is strictly true that no work of
expansion is performed. Nonetheless, material is free to move across the boundary
should expansion or contraction occur, Le., the mass content of the system is
variable. The system is an open system of variable mass with the thermodynamic
consequence embodied in the term IL dp wherein IL is the chemical potential per
unit mass of the substance present in the system. The reader can note that in the
analogous first-law statement written in Section 13.4 as equation (4.2.6), density
was assumed constant, so there dp = 0 and the term IL dp did not appear~
To begin transforming equation (5.1) we assert the compatability of the first
law written for a homogeneous substance in any of the following three forms:
Subscript t refers to total mass and subscript v to unit volume. Total mass is
denoted m,. The quantity dWm denotes differential magnetic work performed on
a unit mass while dW. denotes the differential magnetic work performed on the
total mass. The unprimed quantities Q and U pertain to the unit mass basis. In
equations (5.2) and (5.3) it is assumed that a scalar pressure p exists whose
product with volume change yields mechanical work of expansion, so that a
different treatment would generally be needed for solids. The pressure p must
be assumed field-dependent, reducing to ordinary pressure only in the absence
of the electromagnetic field.
384 Having defined dWm and dW, the next objective is to determine definite
expressions for both. In a reversible process dQ = T dS, dQv = T dSv , and dQ. =
Chapter Thirteen
T dS. where S, S., and S. are the corresponding entropy variables. Using these
variables equations (5.1)-(5.3) can be written as the respective Gibbs equations,
By definition the total quantities are related to the volumetric quantities as follows:
(5.7)
(5.8)
and determine whether this form is compatible within the posited framework. It is
desired that Y, be an extensive variable as are the other differential variables in
equation (5.6) and, correspondingly, that its coefficient X be intensive.
Accordingly, Y, is sought in the form
Y,(TdSv + JL dp + X dY - dUv)
+ dY,(TSv - p + JLP + XY - Uv) = 0 (5.13)
for which it will next be shown that the coefficient of dY, vanishes.
To proceed, dW, from relation (5.11) is substituted into equation (5.6) giving
Because this equation is the sum of products of intensive variables with extensive
variables (still a hypothesis for X dY,) the equation can be integrated along a
path in which mass is added to build up the system from nothing while holding
constant the intensive variables T, X, p, and JL. The result of the integration is
an Euler equation in the form 385
Thermodynamics of
TS. + Xy. - Pv. + p.m. = U. (!1.l5)
Electromagnetism
Neither equation (5.4) nor (5.5) can be integrated in this manner because in them
the volume and the mass, respectively, are fixed at constant values. Substituting
into relation (5.15) from equations (5.7)-(5.9) and (5.12) to eliminate total
variables in favor of the volumetric definitions gives
(5.16)
Comparison of equation (5.16) with (5.13) now confirms that the final term of
relation (5.13) disappears, and what remains can be arranged to read
(5.17)
which supports the hypothesis (5.11). From the definition of y. in equation (5.12),
y. = BV.. Thus, the total work dW. can be expressed as
The combined law for the variable volume and mass system from equation (5.6)
therefore becomes
TdS. + H d(BV.) - p dV. + p. dm. = dU. (5.10)
1
v.=-m"
p
(!l.ll)
+ dm.[ TS + ~B - ; + p. - U] = 0 (5.24)
386 Equations (5.18) and (5.12) enable the Euler relationship (5.15) to be written as
Chapter Thirteen
TS,+ HBy' - py.+ ,.,.m, - U, = 0 (Sol5)
HB p .
TS+---+,.,.- U=O (5.26)
p p
Comparison of equations (5.26) and (5.24) demonstrates that the last term in
,equation (5.24) vanishes and what remains can be expressed as
(5.27)
Comparison of equations (5.27) and (5.5) now identifies the work term in relation
(5.2) as·
(5.28)
This is the central result of our treatment giving dWm as the appropriate work
expression to utilize in diverse problems, such as: compressible flow dynamics,
magnetostriction and other problems with density change; and magnetochemistry
wherein density change and molar transformation occurs. For problems in which
density is constant equation (5.28) reduces to (H / p) dB as previously obtained.
Employing the analogy for an electrically polarizable system developed
previously permits writing the result corresponding to equation (5.28) as
* More generally, from expression (4.3.7) the magnetic work term in equation (5.1) is H· dB where
Hand B need not be collinear. Retracing the derivation then yields dWm = H·d(B/p) in place of
equation (5.28). By the same token the generalization of equation (5.29) gives dW. = E·d(D/p).
These more general expressions are useful in formulating relationships for the ftow of ftuids having
internal structure, such as magnetic colloidal dispersions (see Section 13.9.1},
As an overall check on the work we should find that equation (5.20), which 387
is the most general statement of the combined laws, reduces to the result for
Thermodynamics of
constant mass given by relation (5.27), and to the result for constant volume Electromagnetism
given by equation (5.1). The reductions are readily confirmed in both cases.
Having found no contraditions it may be concluded that our attempt
to determine expressions for electromagnetic work in the variable density,
polarizable systems has been satisfactorily achieved.
Gibbs Equations
Combining the results of equations (5.28) and (5.29) for a constant composi-
tion system of fixed mass containing matter that is magnetically and electrically
polarizable yields a Gibbs equation in the form
(5.30)
Equation (5.20) derived previously expresses the combined first and second
laws for a variable-mass system of one component. That equation is readily
generalized to apply to a system of variable composition by replacing the term
II- dm. by a sum of terms of the form II-i dm" where subscript i denotes a species
of an s-component mixture. Including work of electric polarization along with
the work of magnetic polarization, the broadened relationship is written as
follows:
dtb
e=n- (E.5.1.2)
dt
388 For this geometry the magnetic flux is given by
Chapter Thirteen
cf> = BA+ B'A' (E.5.1.3)
where B is the induction in the inner region, i.e., in the space occupied by the material,
and B' is the induction in the space between the material and the coil. Quantities A and
A' are the inner and outer cross-sectional areas, respectively. In accord with Ampere's
law the magnetic field H is the same in both regions, i.e., H = H', and
H = nill (E.5.1.4)
Eliminating area A and expressing the result as the work done per unit mass gives
1
-dW.
.,.
= Hd - (B) +-d(BoAo)
p".
HI (E.5.1.7)
The first term on the right-hand side is the work done on the inn·e r region per unit mass,
in agreement with relation (5.28). The second term is the work done in increasing the field
in the outer region, normalized to unit mass of the inner region. Any reversible work of
expansion performed by the cylinder equals the work done on surrounding nonmagnetic
material, and the sum of the mechanical work done by the whole system vanishes.
Returning to equation (E.5.1.5) and substituting B' = /LoH' and B = /Lo(H + M),
where M is magnetization of the material in the inner region, gives
Final Boundary
In this representation the system is divided into two subsystems, the matter comprising
the cylinder less the space it occupies, and the total space of the inner and outer regions
located within the coil. The first term on the right-hand side is the density of work done
on the mass; the second term is the work done on the total space, normalized to the inner
mass.
(P.5.2.1)
A=U-TS (6.2)
A=A-BH/p-DE/p (6.3)
The motivation for this definition is that A possesses utility. As usual in thermody-
namics we are free to define any new function. The electromagnetic terms in A
are chosen to yield simple relationships when A is differentiated and combined
390 with the Gibbs equation. We shall see subsequently that A serves as a potential
function, namely, various desired thermodynamic parameters result from partial
Chapter Thirteen
differentiation of A.
Equations (6.3) and (6.2) yield
-
dA = dU - T dS - S dT - H d (B)p - pBdH - Ed (D) DdE
P -P (6.4)
by eliminating dU from equations (6.4) and (6.1) and expanding d (1/ p ) we obtain
- P B D
dA = -SdT+2dp --dH --dE (6.5)
p p p
Comparison of equations (6.7) and (6.5) leads to the following prescriptions for
obtaining entropy S, pressure p, magnetic induction B, and the electric displace-
ment D from function A:
D--p - OA)
(oE (6.8)
T,p,H
It will be assumed that the polarizable fluid is free of the anisotropy that results
from micropolar effects, such as the body couple exerted on molecules or particles
in suspension (see Section 13.9.1). Hence we can assume that M is collinear with
H, and E with D. Thus, we can write
H fH H2 fH
f B dH = P-o( H + M) dH = P-o - + P-oM dH (6.12)
o 0 2 0
and
f"
o DdE
r"
= Jo (60E + P) dE
E2
= 60 2+ r"
Jo PdE (6.13)
(6.14)
Expressions (6.8) with this expression for A yield the following relationships for
pressure and entropy:
P-OH2 60E2)
P=Po+ ( - - + - -
2 2
- u)
+P-o f H(aM dH+ f"(apu)
- dE (6.15)
o au T,H.E 0 au T.H.E
and
S=So+-1 fH(a¥)
- dH+-1 fE(ap)
- dE (6.16)
p 0 aT p.H.E p 0 aT p,H,E
P* = Po + P-o J, H(aMU)
-- dH + J,E(aPv)
- dE (6.17)
o au T,H,E 0 au T,H,E
392 Subtracting this relationship from equation (6.15) gives a simple expression
relating p* to pressure p:
Chapter Thirteen
(6.18)
fJ-oH2 60E2 ) dp
pdU=pTdS+ ( p*-------fJ-oMH-PE -+HdB+EdD (6.19)
2 2 p
which also is obtainable directly from equation (6.1). The form of the Gibbs
equation (6.19) is found to be convenient later in deriving the surface stress
tensor, from which one obtains the equation of motion for a polarizable
fluid.
Another form of the Gibbs equation is useful in treating problems of phase
equilibrium and chemical change in which the thermodynamic system is chosen
as the matter exclusive of the space that the matter occupies.
It is assumed for simplicity that a magnetic field is present in the absence
of an electric field. The objective is to transform the open system form of the
Gibbs equation (5.31) applicable to a multicomponent system. By substituting
for pressure p using expression (6.18) and employing the defining equation
B = fJ-o(H + M), equation (5.31) can be put into the desired form representing
the Gibbs relation for an open system excluding space occupied by the mass.
This relationship is
where ut is the excess of internal energy over the background field energy
associated with the volume y. of space,
(6.22)
Differentiating this expression and eliminating ut with the aid of equation (6.21)
yields
i
dOt = -S, dT + V; dp* - J.toI, dH + L J.ti dmi (6.25)
i=l
The form of equation (6.25) indicates that ot is a function of T, p*, H, and mio
i.e.,
( ao t)
aT = -S" ( aot)
ap* = V;,
TABLE 13.4
Combined First and Second Laws for Various Electromagnetic Systems
Unit mass excluding space Closed TdS - P*d(;) + JLoH d( ~) + E d(;) = dU* Problem 13.5.1
Total mass including space Closed TdS, - pdV, + Hd(BV,) + Ed(DV,) = dU,
Total mass excluding space Closed T dS, - p* dV, + JLoH dI,.m + E dI,.c = dU~
Unit volume of variable mass Open TdSy + HdB + EdD+ JLdp = dUv (5.4)
Total mass excluding space Open TdS, - p* dV, + JLoH dI,.m + E dI'.e + L JL,dm, = dU~ (6.21)
i-I
Unit mass of variable composition Open TdS - Pd(;) + Hd(;) + Ed(7) + t JL,dx, = dU (6.23)
,
Total mass including space Open TdS,-pdV,+ Hd(BV,) + Ed(DV,) + L JL,dm,=dU, (5.31)"
i=l
where Bi is the partial mass entropy of species i, V; the partial mass volume, and
L the partial mass dipole moment.
The chemical potential is a function of temperature T, pressure p*, magnetic
field H, and the masses mi of the s species present. Using the definition of mass
fraction Xi = m;/ m" only (s - 1) mass fractions are independent and the
functional dependence of f.Li can be expressed as
Because T, p*, H, and Xj are state parameters, f.Li is a function of state and its
total differential can be written as
d .=(af.L i) dT+(af.L i ) d *
f.L. aT. p ,H,Xj
aP* T.H,xj
P
(6.33)
1 f.L M s
S dT - - dp* + _ 0- dH + L Xi df.Li = 0 (6.35)
p P i~l
A broad statement of the second law for a system having entropy Ss can be
formulated in terms of the entropy variation dSs written as the sum of two terms,
(7.1.1)
where deS is entropy transferred to the system by its surroundings while diS is
entropy generated within the system.(8) The second law assertion is that diS must
be zero for reversible transformations and positive for irreversible transformations,
(7.1.2)
The entropy supplied, deS, may be positive, zero, or negative, depending on the
interaction of the system with its surroundings. For a system which can exchange
neither heat nor mass with its surroundings, i.e., an adiabatic closed system,
deS = O. For systems which may exchange mass and heat with their surroundings,
deS contains additional terms that can be derived. This is done in Section 13.9,
where diS is normalized to unit volume and time and denoted by the symbol 8.
A system restrained from exchanging heat, mass, or work with its surround-
ings is referred to as isolated. Because an isolated system is a special case of an
adiabatic closed system, it follows that its entropy change in any process must
be nonnegative. In the present section the second law is used in simple form in
reference to isolated systems.
Let us consider a multicomponent, heterogeneous system ~ made up of a
number a of homogeneous, magnetizable phases. Figure 13.4 depicts an isolated
system ~ of the type described located between permeable pole pieces of an
electromagnet. The system is contrained to a constant volume so that no work
of expansion can be performed. The walls enclosing the system are adiabatic and
impermeable so that no heat or mass is exchanged with the surroundings. An
electrical winding of N turns carrying current I establishes a magnetomotiveforce
~ = NI driving a magnetic flux ch. that links the N turns and permeates the
system~ . Associated with an increase offlux d4>~ is electrical work dWe = -~ d4>~ 397
whose value is zero when 4>~ is constant. Thus, a further constraint of constant Thermodynamics of
4>~ is applied to ensure that the system is truly isolated. The constraint can be Electromagnetism
enforced by adjusting the voltage at the terminals of the winding during any
process that takes place. Alternatively, if the winding is a closed circuit super-
conductor, constancy of magnetic flux is guaranteed by Faraday's law and the
properties of the superconductor.
Initially it may be imagined that the a phases are separated by partitions
that are permeable to the magnetic flux 4>~ but impermeable to the flow of heat
or diffusion of species. The material in each of the a regions can be considered
homogeneous and at equilibrium with itself initially. However, the phases may
possibly be at sI1ghtly different temperatures, pressures, magnetic field intensities,
etc., such that, if the partitions are "dissolved," transfer of heat and mass,
displacements of phase boundaries, and redistributions of magnetic field energy
may take place. Applying the fundamental postulate to this process, it is asserted
that the entropy of the isolated system either increases or remains constant,
(7.1.3)
(7.1.4)
h I
r l
, ------0,
::> \
,
I
I
I
I
I N'c ::>
\
e
I I I
____ L.. I ;:> /
...J <: A/
~
(7.1.5)
This indicates that total internal energy decreases in a natural process and is
unchanged in a reversible process for the constraints stated. It follows that with
these constraints of constant total entropy, volume, and magnetic flux, the total
internal energy is a minimum at equilibrium. We shall use the statement (7.1.5)
in the next section to derive criteria of equilibrium in terms of intensive variables
characterizing the phases present within the system.
Another form of the equilibrium criterion is useful in operations in which
temperature T, volume v., and magnetic induction B are held constant. Suppose
the apparatus of Figure 13.4 is modified with a' constant volume thermostatic
reservoir brought into thermal contact with the sample of matter contained
between the pole pieces. An isolated system L can be defined comprising the
sample and the thermostatic reservoir. Writing S~ = St + Sr where St is the entropy
of the total sample and Sr the entropy of the reservoir, criterion (7.1.3) can be
written as
d(St + Sr) 2: 0 (7.1.6)
When a process occurs in which an amount of heat dQt flows into the sample,
the reservoir change of entropy is dSr = -dQtl T. Substituting for dQt from the
first law (5.3) with the mass m, constant gives
The volume V. is constant so that no mechanical work p dV. is done and, because
B also is constant, no magnetic field work H d(BV.) is done. Combining (7.1.7)
with (7.1.6) and rearranging yields the criterion
where At = Ut - TS, is the Helmholtz free energy for the total sample.
Conditions in the isolated system when the partitions are removed will be
analyzed using criterion (7.1.5). The phases become open systems with respect
to each other and we can express dul a ) for the a phase in terms of the Gibbs
equation previously presented in the form (5.31),
dul a ) = T(a) dsl a ) - p(a) dv,a) + H(a) d(B(a)v,a» + L p.~a) dm~a) (7.2.1)
i
Thus, from relationships (7.1.4) and (7.2.1), 399
Thermodynamics of
Electromagnetism
The phase index a takes values 1 to 8, and i is the species index having values
1 to s. Expanding dU~ gives
The individual variations dS;I), etc., are subject to the constraints of constant
total entropy, constant total volume, constant total mass of each species (chemical
reaction excluded), and constant total magnetic flux. From the entropy, volume,
and mass constraints we have
The magnetic constraint is absent from the above list. This constraint can be
specified in alternate ways, and we shall see that the orientation of the field and
geometric arrangement of the phases influence the result obtained.
Normal Field
It will first be assumed that the phases are arranged in layers, each of a
uniform thickness, with the magnetic flux oriented normal to the layers, as
sketched in Figure 13.5. Using the condition that magnetic induction is continuous
across an interface, we can write
(7.2.5)
400 where B is the uniform value of magnetic induction in all the phases. Thus, the
magnetic induction can be factored out of each differential term in which it
Chapter Thirteen
appears in equation (7.2.3):
(7.2.6)
This summation of internal magnetic energy changes in general does not sum to
zero, even though the electrical work done on the system by the external circuit
is nil. A portion of the magnetic field energy is converted to the other energy
forms, or vice versa.
Collecting terms having the common factor V: a ), the expression for dU~
can be written as
Equation (7.2.7) has 8(s + 2) independent variables while the number of con-
straints from system (7.2.4) is s + 2. The expression for dU~ may be expressed
in terms of s + 2 fewer independent variables by using the constraining equations
to eliminate, for example, dSP), dvl 1 ), and the s quantities dn~l). The result yields
an expression for dU~ in terms of (8 - l)(s + 2) truly independent variables. The
Here, the variations dsl2), dV?>' dm~2), dm&2), etc. are truly independent. There-
fore, at equilibrium in the closed system, by using the second-law result that U~
is minimum, and employing the necessary mathematical criteria characterizing
an expansion of a function of multivariables(4) it follows that
(7.2.10)
These criteria have the same appearance as the standard results for unpolarized
systems, i.e., temperature is uniform in the system, and the chemical potential
of any given species has the same value in every phase. But, in addition, at
internal equilibrium with respect to boundary displacement, we also obtain the
following result on pressure:
where definition (6.18) for p* has been introduced. Thus, the pressure can vary
across a flat phase boundary only when there is a difference of the normal
component of magnetization.
From the analogy between electrostatic and magnetostatic systems, the result
(7.2.11) translates for electric systems to
(7.2.13)
and the pressure can vary across a flat phase boundary only when there is a
difference of the normal component of polarization P.
Tangential Field
It is now assumed that the phases are arranged in layers that are tangential
to the direction of the field; see Figure 13.6. From Ampere's law the tangential
component of magnetic field is continuous across a boundary between phases:
(7.2.14)
The general relationship (7.2.3) for dU~ can be particularized to this special case,
recognizing that while the overall size and shape of the vessel containing the (}
phases is unchanged, the boundaries between phases shift and so the cross-
sectional area A;a) of the phases varies with an exchange of species from one
phase to another. We represent the volume of a phase a as vl a) = Ala)/;a) where
l?) = W) = ... = W) = I is the fixed distance between the pole faces of the
permeable yoke. Adding together the magnetic terms of expression (7.2.8) and
--:-1
I
I
V-system ~
I
I
I H~I=H")= ... =H")
I
I
I
I
I FIGURE 13.6. Isolated system of fI
- --+-"'_""':.JI homogeneous, layered phases with
orientation of magnetic flux tPI. tangen-
tial to the layers.
substituting these relations yields 403
HI d(B(1)A(1) + B(2) A(2) + ... + B(8)A(8» Thermodynamics of
Electromagnetism
= HI d(c/J(I) + c/J(2) + ... + c/J(8»
=Hldc/J=O (7.2.15)
where the constraint c/J = constant initially imposed on the system was employed.
Thus, the sum of the magnetic terms vanish, indicating that for this tangential
field system there is no net conversion of magnetic field energy to the other forms.
The remainder of the argument proceeds as in the case of normal field
orientation developed previously and results again in the equilibrium criteria
(7.2.10). In addition, with tangential magnetic field the pressure as well as the
temperature and chemical potential of each species are uniform throughout the
system, similar to conditions in unpolarized matter. Then p(J) = p(2) = ... = p(9),
or equivalently, because of the continuity of the tangential magnetic field intensity,
p*(I) = p*(2) = ... = p*(8) (tangential field) (7.2.16)
For a given orientation and intensity of the field, fixed mass ratios of the
species, and given temperature and external pressure, the equilibria remain the
same, regardless of the constraints, for we assume that local conditions govern
the distribution of species among the phases and the variation of pressure from
phase to phase. The constraints chosen for the derivation were selected for
convenience and not as a necessity. For example, if the magnetomotive force ~e
rather than the magnetic flux c/J~ were held invariant, the criterion that U~ is
minimum would be altered, but the final results (7.2.10) and (7.2.11) or (7.2.16)
are unchanged.
When the species in the system react chemically with each other, more
elaborate derivations are required to establish the equilibrium criteria.
An Experimental Verification
The relationships (7.2.12) and (7.2.16) are manifested in measuring pressure
in magnetizable fluids using a thin flexible liquid-filled sensor connected to a
manometer.(6) If the sensor surface is oriented perpendicular to the field, the
manometer registers a pressure that is larger by the magnitude JLoM2/2 than
when the sensor surface is oriented tangential to the field. Denoting the pressure
difference by t:.p, the magnetization of the fluid is given as M = (2t:.p/ JLO)I/2.
Figure 13.7 shows curves of the magnetization of a ferrofluid comprising collodial
magnetite in kerosene, calculated from pressure measurements parallel and per-
pendicular to the field. Values of magnetization determined with a ballistic
galvanometer are plotted on the curves for comparison. It can be seen that the
agreement between the two methods of measurement is close, aside from what
appears to be a small systematic difference.
The same pressure jump mechanism accounts for the behavior of a magnetic
fluid drop surrounded by nonmagnetic fluid and subjected to a uniform applied
magnetic field. An equilibrium is established between the jump and capillary
404 pressure due to curvature of the drop surface leading to elongation of the drop
in the direction along the magnetic field.
Chapter Thirteen
The steps to obtaining the relationship /:l.p = /LoM2/2 are as follows. Let (2)
denote a position outside the magnetic fluid, hence within the nonmagnetic
manometer fluid, and (1) a position inside the magnetic fluid; while subscripts
nand t denote normal and tangential orientation of the sensor interface relative
to the field. Then relationships (7.2.12) and (7.2.16) can be stated as
P*(1)
n
+ /Lo
2
M(1)2 = p*(2) + /Lo M(2)2 = P
n 2 e.n (7.2.17)
and
(7.2.18)
where it is recognized that M~2) = 0, p!(2) = Pe.n, and pt(2) = Pe., in the nonmag-
netic manometer fluid. Manometer fluid pressure with normal orientation of the
field has been denoted by Pe.n, and Pe., denotes the manometer fluid pressure
with tangential field orientation. From its definition (6.17) p* is a scalar quantity,
hence for a constant value H of the field p!(l) = pt(l) and subtraction of equation
(7.2.17) from (7.2.18) gives
(7.2.19)
Let us consider two phases denoted by (1) and (2) in equilibrium with each
other in the presence of a magnetic field. The criteria of equilibrium with respect
to transfer of species, from system (7.2.10), requires equality of the chemical
potential of each ith species in the separate phases:
(8.1.1)
(8.1.2)
.1,
For a pure species .4lS =g, .4lV = 'Y, and .4llm = where a script font denotes
molar, subscript m denotes magnetic, and .4l denotes molecular weight. Thus,
from relations (8.1.2) and (6.34) with dxj = 0,
Tangential Field
When the magnetic field is oriented tangentially to the interface between flat
layers of two phases, the criterion (7.2.16) for mechanical equilibrium requires
p(1) = p(2). From expression (6.18), recognizing that T(1) = T(2) = Te and H(1) =
H(2) = H. = Bel 11-0 , where Be is the applied induction field, for a system in
equilibrium at the environmental pressure Pe
aT) = _(.1(2)
(aBe P.
- .1(1»)
g(2) _ g(1) (8.1.5)
(8.1.6)
406 Normal Field
Chapter Thirteen
The mechanical equilibrium condition (7.2.11) is i l ) - H(I) B(I) =
p(2) _ H(2) B(2), from which it follows [see equation (7.2.19)] that an equivalent
statement is
(8.1.7)
where
(8.1.8)
(
aT) = _(.1(2) - .1(1»)
(8.1.10)
aBe P. y(2) - y(l)
where A is the molar latent heat. The molar moments are approximately given by
(E.8.l.l)
and
(E.8.t.3)
where XCv) and x(l) are mass susceptibilities defined as volumetric susceptibility divided
by density and, as previously defined, .4l is the molecular weight. Thus equation (8.1.8)
can be written in the form
(E.8.1.4)
The susceptibilities and A decrease with an increase in temperature. Assuming that suitable
average values can be chosen, the integration of this equation gives
T(H)
- - = exp [B;.4l
- - - (x (v) - x(l) ] (E.8.1.5)
T(O) 2P,oA
Data
A = 75.5 J mor l K- I
T(O) = 90 K (atmospheric boiling point in the absence of a field)
XCv) = 4.345 X 10-6 m3 kg- 1
X(I) = 2.920 X 10-6 m3 kg- 1
Denoting the ith chemical reactant by Ri the reaction can be rewritten compactly
as
s
0= L ViRi (8.2.2)
i=1
where Vi are whole number stoichiometric coefficients and s is the total number
of species. The values of Vi for species that appear on the left-hand side of
equation (8.2.1) are thereby assigned negative values. Let us consider a reaction
that proceeds a differential amount and denote the change in mols of the general
species i as dni' From relation (8.2.1) the ratio of mole change to stoichiometric
coefficient is the same for all the species:
Using relationship (8.2.3), the internal energy is dUt = I; lI;iL;.M; dt, and applying
criterion (7.1.5) with the equal sign in the form a Uti at = 0, we obtain the general
criterion for the chemical equilibrium,
aUt
ag = ~ lIiiL;.M; = 0
S
(8.2.7)
The relationship of the second equality displays the usual form for reactions
unaffected by a field. However, in the present case the chemical potentials iL; are
magnetic-field dependent and so integral expressions are next developed for the
chemical potential by integrating the differential form (6.34);
_ _
diL; = -S; dT + V; dp* - iLol; dH
_ +I
S-l(a~iL ;) dXj (8.2.8)
j uXj p*,H,T,nj
When applying equation (8.2.8) to one mole of a pure species in the absence of
a magnetic field, .MS; = g, .MY, = 'Y, .Ml, = off = 0, p* = p, dXj = 0 for all j, and
diL; = diL where .M is the molecular weight. Hence
(8.2.11)
410 where Po is a reference level of pressure at which /.£ = /.£o(T). Integration between
the indicated limits yields
Chapter Thirteen
( °
RT p / po
/.£ T,p,H=O)=/.£ (T)+-:ijln (8.2.12)
(8.2.13)
(8.2.14)
.1. = -1
A
I HO'
H
i
.1dH
- (8.2.16)
where ji denotes the partial molar magnetic moment of the ith species.
The function of integration /.£i( T, p, H = 0) in equation (8.2.15) is given by
expression (8.2.13). Thus, the chemical potential for a component of the gas
mixture can finally be expressed in the form
(8.2.17)
(8.2.18)
(8.2.19)
where
s
Kp IT p;'
= i=1 (8.2.20)
where IT;~l denotes the product of the factors; Kp is well known as the definition
of the equilibrium constant. Because JL?( T) is synonymous with free energy per
unit mass of the pure species at the reference pressure [set G~ = G t for H = 0
in the last equation in system (6.28)], the quantity L;~l ViAtiJL?( T) in equation
(8.2.19) is conventionally denoted as the standard change of free energy .6.G~ of
the reaction at temperature T. Quantity .6.G~ is the standard free energy change
accompanying total conversion of a stoichiometric amount of reactants to
products in the absence of a field. With this nomenclature relationship (8.2.19)
can be written as
where
.6.G(B) = -RTIn Kp(B) (8.2.22)
s
.6.G~ = - L VijiB (8.2.24)
i=1
Assuming the radicals are present as a gas phase, an equilibrium constant can be written
as
(E.8.2.2)
From equation (8.2.21), recognizing that for this system .Ii takes only two values,
(E.8.2.3)
where .9'f is the molar moment of an up spin and .9'~ the moment of a down spin. The
value of Kp(O) is 1, because the. number of up and down spins in a given direction is
equal in the absence of an applied magnetic field. Rearranging the equation and using
relation (E.8.2.2) thus gives
(E.8.2.4)
If it is assumed that the magnetic moment of a spin is equivalent to one Bohr magneton
ILB' we obtain (J!f - J!~) = NILB - (- NILB) = 2NILB where N is the Avogadro number.
Thus,
(E~.2.5)
where
(E.8.2.9)
The product /LoB measures the energy of one spin in the field, and ko T the thermal energy
per particle. This relationship shows that the dimensionless ratio of these energy terms
determines the fractional saturation.
The molar absolute value of the radical's magnetization at saturation is 45.9% that
of iron, for which the Bohr magneton number is 2.18 at room temperature. Calculated
values of the fractional saturation vs. applied magnetic field for several values of absolute
temperature T are shown in Figure 13.8.
The dot indicates the presence of an unpaired electron in the molecular fragment or atom.
From the prior discussion the unpaired electron carries a magnetic moment, and so the
free radicals are magnetizable. In the presence of an applied magnetic field a fraction a
of the free radicals has magnetic moment aligned with the field while the remaining
fraction (1 - a) is aligned against the field. The net moment per mole !fi =
(E.8.3.1)
aG~ = -2jB
= -2/Lo IH .1 dH (E.8.3.2)
where definition (8.2.16) was introduced with j assumed equal to 9>. Equation (E.8.2.8)
yields
B)
/LB-
.1 = .1, tanh ( - (E.8.3.3)
kBT
Thus
where .1, = N/LB, and a = /LBB/kBT as defined previously. The integral above is listed
giving
aG~ = - RT In cosh2 a (E.8.3.5)
where
(E.8.3.7)
(E.8.3.8)
Under conditions where the extent of dissociation is small, PCH 4 (B) = PCH 4 (O). Then the
increase in free radical partial pressure in the field is given by
Table 13.5 lists results of computation for the dissociation of methane using this formula.
As the field increases, the magnetization of the product free radicals approaches saturation
far in advance of substantial conversion of the methane to free radical products.
TABLE 13.5 415
Methane Dissociation in a Magnetic Field (298 K)
Thermodynamics of
Electromagnetism
B (tesla) a Fractional saturation Free radical ratio
0 0 0 1.000
200 0.4508 0.4225 1.l03
400 0.9016 0.7171 1.435
600 1.352 0.8745 2.062
800 1.803 0.9471 3.116
1000 2.254 0.9782 4.815
2000 4.508 0.9998 45.38
00 00 1.0000 very large
Explosively compressed magnetic fields have generated pulse field intensities in excess
of 11r tesla. Fields of Hf tesla are found in magnetic white dwarf stars while pulsars give
indication of field strength equal to about 108 tesla. (31)
Water is too stable to be easily decomposed at moderate temperatures into hydrogen
and oxygen according to
However, because oxygen is paramagnetic while water and hydrogen are not, application
of a magnetic field to water tends to enhance the reaction, thus extracting oxygen. Cur1(30)
studied the thermomagnetochemistry and concluded that a field in excess of 10· tesla is
required. While this field level is daunting the study holds interest for the engineering
problems that it addresses. For example, the oxygen produced is forcefully attracted by
the field so that its removal requires expenditure of energy.
At=Ut-TSt (P.8.2.1)
and the Gibbs equation (5.31), derive the relationship applicable to a binary mixture,
(b) For conditions of constant temperature T, magnetic induction B, and total volume V" derive
the following relationship for free energy per mol from equation (P8.2.2),
(P.8.2.3)
(c) An expression relating chemical potential to magnetic field intensity and the partial pressure
of a species in a perfect gas mixture was developed as equation (8.2.17). Assuming Raoult's law is
obeyed in the form p, = p~c" where p~ is the vapor pressure of pure liquid species i and c, is the
mol fraction in the liquid mixture, show that the chemical potential for unit mass of species 1 in the
liquid mixture is given by
(P.8.2.4)
where 9, is defined by expression (8.2.16), and that a similar relationship applies for species 2.
416 (d) Using the results of (c) and (b) above, show that the/ree energy o/mixing per mole of liquid
mixture is given by the expression
Chapter Thirteen
(P.8.2.5)
where silO = (c,.4l'/L~ + C2.4l2/L~) + RT(c,lnp~ + c2 1n p~) is the free energy of the amount of the pure
components making up the mixture.
Show that the magnetic terms on the right·hand side of expression (P.8.2.5) reduce to
-(/LoH 2/2)(c,xl l ) + C2X~I») when the molar susceptibilities XII) and X~I) can be assumed constant.
It is seen from expression (P.8.2.5) that the free energy of mixing is negative and decreases with
increasing intensity of the applied magnetic field.
There are terrible problems said the doctor who performed the
first human heart transplant in 1968. "The main one is to
develop an inexhaustible, implantable, non-heat-producing
power source of energy." If so he speculated, "It would be in
autos first, then refrigerators and finally in biological devices. "
The New York Times, January 13, 1988
and with the defining equation B = JLo(H + M) the differential of the magnetic
induction can be expressed as
Substitution of expressions (8.3.4) and (8.3.2) into equation (8.3.1) and collecting
common terms yields the differential of heat added dQv as
(8.3.7)
which simplifies to
(8.3.8)
418 For a reversible process dSv = dQvl T, so from equation (8.3.5) dSv is expressed
as
Chapter Thirteen
Because entropy is a function of state, its differential is also exact. Hence equation
(8.3.9) yields
(8.3.11)
(8.3.12)
K=-e~L (8.3.13)
From equation (8.3.12) with K taken as constant, it can be seen that the specific
heat becomes independent of the field intensity,
(8.3.15)
Integration of equation (8.3.9) using the above and further assuming c(T) = Co
is constant gives an explicit expression for the entropy of the ferromagnetic
substance:
Sv = Co In T - lLoKH + constant (8.3.16)
The first term on the right-hand side displays the familiar logarithmic increase
of entropy with temperature.
EXAMPLE 13.4. Cooling with Adiabatic Demagnetization of Elemental Gadolinium 419
Consider the process of temperature reduction that occurs when a magnetic substance
is rapidly removed from a region of magnetic field (adiabatic demagnetization). Denoting Thermodynamics of
Electromagnetism
initial conditions by subscript i and final conditions by f, expression (8.3.16) with (Sv)i =
(Sv)' yields
(E.8A.I)
If the material is the ferromagnetic element gadolinium (Gd) at its near room temperature
Curie point, we have 1i = 8 = 295 K, Co '" 4.2 x lIf J m-3 K- J , and K = 29,500 A m- J K- J
(370 gauss K- J ). If the magnetic induction B = P-oH = 7 T (70,000 gauss), such as is
routinely produced with superconducting magnets, the adiabatic temperature decrease is
(Ti - T,) = 14 K.
Figure 13.9 illustrates experimental values of the isentropic temperature change
produced by applying a 7 T field to a Gd sample at various initial temperatures. The effect
persists above the Curie temperature 8e because any material that is ferromagnetic below
8e is paramagnetic above 8e • The peaked shape of the curve is related to the changing
value of the pyromagnetic coefficient. Brown(17) computes a thermodynamically determined
curve showing a reasonable match to the data of Figure 13.9, using the known spin state
of 7/2 for gadolinium to estimate M(T,H).
(P.8.3.I)
g 18
~ 14
e~
,,;
f 12 00
!() 0
\
I
10
I!
i"
00
8 0
l 0
0
E
. 8 ~
f! of} 00
00
FIGURE 13.9. The isentropic temperature A. 4 0 0
change produced by applying a 7 tesla mag- ~ 2
netic field to elemental gadolinium (after J 200 240 280 320 380
Brown(I7). Initial Tempenltu.. (I<)
420 rotates continuously. Give a mechanistic explanation of this phenomenon and a thermodynamic
explanation in terms of the construction (Mollier diagram) of Problem 13.8.3.
Chapter Thirteen Analysis(S) of the conversion of heat to work for a particular recuperative cycle shows that the
efficiency can approach that of a Carnot engine which no heat engine can exceed.
(9.1.1)
(9.1.2)
The components Til' T22 , and T33 perpendicular to the planes are the normal
stresses; those acting in the planes are shear stresses. The latter include all the
remaining stresses: T\2, T13 , T210 T23 , T310 and T32 •
422 A balance of energy for a fixed mass of variable shape, velocity, position,
and temperature can be written as the following integral relationship, equating
Chapter Thirteen
the rate of increase of energy of the mass to the rate at which work is done on
the mass by surface and body stresses less the rate at which heat is removed plus
the rate at which electromagnetic energy is transmitted in:
~J
dt 9'1
p(V+V2)dV=J tn.VdS+J pg·vdV
2 9'1 9'1
-r Ja9'1
q. 0 dS - r
Ja9'1
o· (E' x H') dS (9.1.3)
fa9'1
(tn· v) dS = f
a9'1
(0· T· v) dS = f a9'1
(T· v) ·0 dS
= L V· (T·v) dV (9.1.4)
-L Vx[(vxB)xH]dV= L H·[Vx(vxB)]dV
-d
dt m
ipUdV= dU
p-dV
m dt
f (9.1.8)
-d
dt
im 2
v .
p-dV=
2
fm 2
d(v /2)
p---dV=
dt
fm dv
pv·-dV
dt
(9.1.9)
When the results (9.1.6)-(9.1.9) are substituted into equation (9.1.3) and the
arbitrariness of the volume of integration is invoked, the following equation is
obtained after minor rearrangement:
dU ( p--V·T-pg
p-+ dv ) ·v=T:Vv-V·q-H·[Vx(vxB)] (9.1.10)
dT dt
This differential equation for the balance of energy is not yet expressed in its
simplest form. To proceed further the momentum balance for the chosen mass
of fluid will be formulated. Applying Newton's law of motion for a continuum,
the integral momentum balance reads
f pv dV =
ddtJm f t dS + f pg dV (9.1.11)
Jam Jm
which transforms to
dv
p-=V·T+pg (9.1.11)
dt
Inspection of this equation shows that the bracketed terms on the left-hand side
of equation (9.1.10) disappear, leaving the following differential equation
expressing the balance of internal energy:
dU .
Pdi= T:Vv-V·q-H·[Vx(vxB)] (9.1.13)
It is noteworthy that the kinetic energy and body force terms have dropped out
of the equation, a consequence of subtracting the mechanical energy terms.
424 Dividing each term of the Gibbs equation (6.19) by dt and omitting field
terms other than the magnetic ones gives, with slight rearrangement,
Chapter Thirteen
dS dU (JLOH2
pT-=p-- p*----JL MH ) -dp- HdB
- (9.1.14)
dt dt 2 0 p dt dt
This Gibbs equation provides a means for computing entropy rate of change
when all other terms including dU / dT are known. The relationship (9.1.13),
which also contains dU / dT, is derived with reference to an arbitrary irreversible
process. Assuming that both equations are valid, it is possible to eliminate the
term p dU / dt between them and obtain an equation for the entropy production
rate. As an adjunct to carrying out this step the equation of mass conservation
is needed. In differential form, valid for a compressible medium, it reads
ap
-+V·(pv)=O (9.1.15)
at
Because V·(pv) = v·Vp + pV·v, equation (9.1.15) can be rewritten as
dp
- = -V·v= -1:Vv (9.1.16)
pdt
ii:Vv
=j.(i·V)v
= avx
ax
Likewise (j j): Vv = av.,/ ax and (k k): (Vv) = avz / az. Summing the separate terms yields
(QED)
where v, as previously, is the velocity of the mass at the point in question. Using
the vector identity
dB ilB
- = - - B(V 'v) + (B· V)v - V x (v x B) (9.1.20)
dt ilt
If it is assumed that B is temporally constant, then the first term on the right-hand
side of this equation disppears. Thus
dB
H- = -B·H(V 'v) + H·(B·V)v - H·V x (v x B)
dt
= -BHI:Vv+ HB:Vv- H·V x (v x B)
= (BH - BHI):Vv- H·V x (v x B) (9.1.21)
dS
pT- = cI> - V·q (9.1.22)
dt
with Tm given by
Constitutive Relationships
As a general statement, the rate of entropy increase in a mass offixed identity
equals the rate of internal production of entropy plus the rate at which entropy is
t The stress balance at a planar interface between media using expression (9.1.25) is found to be
given by continuity of p* + !LoM~/2, where Mn is the normal component of magnetization evaluated
adjacent to the interface, in agreement with the mechanical equilibrium criteria of Section 13.7 (see
Reference 5, p. 129).
transported into the mass. This balance statement is expressed mathematically as 427
(see notation of Figure 13.10).
Thermodynamics of
Electromagnetism
~
dt
r pSdV= J9'r1 6dV+ Ja9'r 1 j,'DdS
J9'1
(9.1.26)
in which 6 is the internal rate of entropy production per unit volume and j, is
the entropy flux vector. Applying the Reynolds transport theorem, transforming
the last term using Gauss's divergence theorem, and noting the arbitrariness of
the volume chosen for integration, we obtain the differential equation equivalent
to equation (9.1.26),
dS •
6=p--V'J (9.1.27)
dt '
dS
6 = p-+ V·(q/T) (9.1.28)
dt
When the fundamental postulate of the second law is applied to a unit mass of
the moving fluid, it follows from the discussion in Section 13.7 that 6 is
nonnegative:
6~0 (9.1.30)
q. V In(1/ T) ~ 0 (9.1.3la)
FIGURE 13.10. Integral control volume for deriving the entropy balance equation.
428 and
Chapter Thirteen (9.I.3Ib)
(9.1.32)
K
T2 (VT) ·(VT) 2:: 0 (9.1.33)
(9.1.34)
(9.1.35)
(9.1.36)
L pG·..,dV (9.1.37)
(9.1.38)
Again invoking the concept of Cauchy a couple stress tensor C is defined such
that c" = n' C. Then, following the same mathematical steps given in equation
(9.1.4), it can be seen that the surface integral transforms to a volume integral
given by
r
J'fJ1!
Cn ' ' ' ' dS = r V.(C·",) dV
JfJ1!
(9.1.39)
These expressions of couple work give additional terms that must be added to
the right-hand side of equation (9.1.3) in treating the problem of fluid with
intrinsic angular momentum. A term modeling the rotational kinetic energy of
spinning particles is added to the accumulation term on the left-hand side.
The foregoing indicates an approach to this topic that yields a formulation
of the governing 'relationships complete with constitutive relationships for mag-
netic couple stress and intrinsic angular momentum conversion rate. (26) However,
issues concerning the role of magnetic relaxation remain to be clarified. Experi-
mental studies of related flow fields using ferrofluids are emerging.(27) Analyses
of a number of flow fields with couple stress are reviewed in the literature. (5.32)
(E.9.2.1)
{E.9.2.2}
{E.9.2.4}
Let us consider one plate of the electrode pair in Figure 13.1. A control volume that
straddles the upper electrode is free of field on its top surface, while a uniform field is
present over the lower surface and is oriented normal to the surface. We can imagine that
the electrode is slightly lifted away from the dielectric, with the lower surface of the control
volume located within that space; in this case the free space form of To given as expression
(E.9.2.4) is applicable. Because the unit normal 0 on the lower surface is parallel to the
field, the stress vector tn is obtained in the form
{E.9.2.5}
(E.9.2.6)
Here tn is positive, giving a tensile stress acting to pull the electrode toward the dielectric
slab. The slab in tum is under compression.
In both these cases the field source serves as a "bottle" which must support a stress
to "contain" the field within it. The magnitude of these stresses corresponds identically
to the expressions for field energy density developed in Section 13.4. Because a stress level
of one atmosphere equals 1.013 N m-2 , the values of Av in Table 13.3 can immediately
be converted (except in one case) to equivalent stress in atmospheres or psi; see Table 13.6.
The exceptional case is that of the ruby mica capacitor. The energy density Av listed
applies for the dielectric and not the thin air gap. Because the displacement .Q is contino
uous, BoEg = BEd where subscript g denotes gap, d dielectric, and thus (Av)gap =
(Av)dioloeuie X B/ Bo.
The very large magnitude of the wall stress for the future superconductor poses a
formidable challenge to the designer. One investigator employs a series of discrete, coaxial
TABLE 13.6 431
Computed Values of the Electromagnetic Wall Stress (Systems of Table 13.3)
Thermodynamics of
Wall stress Electromagnetism
cylindrical windings said to limit the bursting stress in any cylindrical layer; using ordinary
conductors and pulse operation to limit the temperature rise, a magnetic field of 100 tesla
is generated nondestructively.(29) In principle, a high-temperature superconducting magnet
of this design could operate continuously.
In Section 13.9.1 the Gibbs equation for a homogeneous fluid was manipu-
lated to obtain an equation for the rate of entropy production, yielding along
the way the magnetic stress tensor and, with assertion of the second law, allowable
forms of constitutive relationships for viscous stress and heat flow. This section
introduces the Gibbs equation for a fluid mixture and employs the corresponding
strategy to derive relationships for diffusion rates of magnetizable species in a
mixture subjected to a magnetic field. Standard treatments(S) of diffusion in
external force fields are inappropriate to this situation in which the component
electromagnetic force densities are unknown a priori. '
From the Gibbs equation (6.23) applicable to mixtures, the rate of change
of entropy per unit mass can be expressed as
(9.2.1)
Introducing the definition of p* from equation (6.18) and the defining equation
B = ILo(O + M), the above equation can be expressed as
dS dU ILoH2(*) dp dB s dx;
pT-=p-- p ----ILoHM - - H - - L I L J J - (9.2.2)
dt dt 2 pdt dt ;=1 dt
This relationship for entropy production rate extends that of equation (9.1.14)
with the addition of the last term in equation (9.2.2) giving the contribution of
composition rate of change.
An equation for conservation of species i can be developed in reference to
an integral balance on a control volume whose bounding surface moves at the
local mass average velocity v. The mass rate of accumulation of species j within
432 the volume is (d/ dt) 1PXi dV and equals the transport rate of the species into
the volume by the process of diftusion across the bounding surface. The latter is
Chapter Thirteen
given by -1 JiB dS where J i is the mass flux vector of species i relative to the
plane of no net mass flux,
The mass average velocity V is defined in terms of the species velocities Vi and
mass fractions Xi,
s
v= L
;=1
ViXi (9.2.4)
Applying the Reynolds transport theorem to the volume integral and Gauss's
divergence theorem to the surface integral, the arbitrariness of the volume gives
the species conservation equation as
(9.2.5)
(9.2.7)
and
11--
-~V·J- =J-'V ~ (11--) -V, (11--)
~J- (9.2.8)
T ' 'T T'
With these expressions the entropy increase rate in equation (9.2.6) can be written
in desired form as
dS
p-= -V·
dt T
1 , (-1) -
[q, - L JilLi] +-Tv:Vv+q'V
T T
Ls
;=1
J;'V (11-1)
-
T
(9.2.9)
This equation can be compared to the form of the entropy balance equation 433
(9.1.27)
Thermodynamics of
Electromagnetism
dS V •
dt= 9+ 'J s
P- (9.2.10)
from which we identify the entropy flux is and internal entropy production rate
8 as
(9.2.11)
and
1 , ( -1 ) - ~
9 =-Tv:Vv+q'V L.. J,'V (IL')
- (9.2.12)
T T '=1 T
Alternatively, the internal entropy production rate can be expressed in the form
s
T9 =Tv:Vv-is·VT- 1:
i=l
J"VILi (9.2.13)
This expression displays the characteristic form with sums of the products of
fluxes and their driving forces on the right-hand side. The fluxes are respectively
the momentum flux Tv, the entropy flux is, and the mass fluxes of the s species
J,.
T8 = - f
i=1
Ji,VIL, (9.2.14)
(9.2.15)
By their definition the mass fluxes J 1 and J 2 are not independent of each other.
From expressions (9.2.3) and (9.2.4), J 1 + J 1 = 0 and so
(9.2.16)
This expression for entropy production rate has the same appearance whether
or not a field is applied. However, because the chemical potentials are field
dependent, the influence of a field is indeed inherent in the expression.
434 By referring to equation (P.8.2.4) it can be seen that chemical potential ILl
depends on temperature T, mol fraction c;, magnetic field H, and somewhat on
Chapter Thirteen
total pressure, as the latter affects the vapor pressure of a pure species. Neglecting
the pressure effect, the gradient V(ILI - IL2) can be expanded for an isothermal
system to give
(9.2.17)
From the cited expression for chemical potential of a liquid mixture, the
coefficients in the above expansion are calculated to be
(9.2.18)
and
(9.2.19)
where ""-j is the molecular weight of species i and J is the partial molar moment.
j
From equation (9.2.16) the form of the linear constitutive law guaranteeing that
(1 2: 0 is
(9.2.20)
(9.2.21)
(9.2.22)
(9.2.23)
and
( 1 + 1)
""-ICI ""-2 CZ =
J1
XIX2
(9.2.24)
Substitution into equation (9.2.21) to eliminate the mol fraction variables gives
(9.2.25)
In the absence of a magnetic field J I is conventionally represented as J I = 435
- Dp VXl> where D is defined as the binary diffusion coefficient. Thus, from
Thermodynamics of
relationship (9.2.25), with H = 0, L = Dp.J,{I.J,{2 ill RTxIX2, and elimination of L Electromagnetism
from equation (9.2.25) yields
(9.2.26)
(9.2.27)
Setting the partial molar magnetic moment equal to that of the pure species
il =.11 yields a form employed by Blums et al.(9,33) in the study of colloidal
magnetophoresis.
(E.9.3.1)
Assuming that the partial molar moment equals the molar moment of the pure species,
i, = .i, where .i, = M, V = X,HV and 'V = At/ P is the molar volume. Substitution into
equation (E.9.3.1) and rearranging gives
(E.9.3.2)
Integration of the left-hand side between positions at the two ends of the tube gives
(E.9.3.3l
(E.9.3.4)
436 Thus, the separation factor is found from equation (E.9.3.2) in the form
Chapter Thirteen
(E.9.3.5)
Separation can occur only when there is a difference in the magnetic susceptibilities ..
Separation is favored by a large ratio of magnetic energy density (XI - X2)lL oH 2/2 to
thermal energy density RTI 'Y.
Retrospective
The chemical engineer may be called upon to design a process containing
polarizable matter which must operate in a region of strong magnetic or electric
fields. Although some of the thermodynamic effects are normally so small as to
be negligible, careful design practice requires that anticipated effects be evaluated
and not merely assumed to be small. This chapter presents analyses by which
several magnetic and electric effects may be evaluated. Shifts of equilibria in the
largest attainable magnetic fields exceed the sh~fts attainable in the largest electric
fields.
Present day engineering concepts in which fields do play an important role
include field energy storage systems, systems of heat and work interconversion,
fluid mechanics with ferro- and paramagnetic species, and processes of mass
transfer with polarizable species.
Recent advances in superconductivity enhance the interest in the phenomena
utilizing magnetic fields. Creative use of the basic principles and mechanisms
discussed can be expected to yield future innovations.
LITERATURE
REFERENCES