I
Vrriag von Wilhelm Engelmann, Leipzig".
Meisenbach Riffarth. &_ Co., Leipzig.
THE
SCIENTIFIC PAPEKS
Vx*
J.° WILLARD GIBBS, PH.D., LL.D.
»«i
FORMERLY PROFESSOR OF MATHEMATICAL PHYSICS IN YALE UNIVKRSITY
TWO VOLUMES
VOL. I.
THERMODYNAMICS
WITH PORTRAIT
LONGMANS, GREEN, AND CO
39 PATERNOSTER ROW, LONDON
NEW YORK AND BOMBAY
1906
All rights reserved
f:
113
GW
Permission for the present reprint of the different
papers contained in these volumes has in every case
been obtained from the proper authorities.
\
PKEFACE.
WITH the exception of Professor J. Willard Gibbs's last work,
Elementary Principles in Statistical Mechanics* and of his lectures
upon Vector Analysis, adapted for use as a text-book by his pupil
Dr. E. B. Wilson,*f and printed like the former as a volume of the
Yale Bicentennial Series, none of his contributions to mathematical
and physical science were published in separate form, but appeared
in the transactions of learned societies and in various scientific
journals.
These scattered papers, which constitute the larger and perhaps
the more important part of his published work, are here presented
in a collected edition, from which, so far as known to the editors,
no printed paper has been omitted. A small amount of hitherto
unpublished matter has also been included. Permission for the
present reprint of the different papers contained in these volumes
has in every case been granted by the authorities in charge of the
publications in which they originally appeared, a courtesy for which
the editors desire here to make due acknowledgment.
In the arrangement of the papers a grouping by subject has been
adopted in preference to a strict chronological order. Within the
separate groups, however, the chronological order has in general
been preserved.
The papers on Thermodynamics, which form somewhat more than
one half of the whole, constitute the first volume. Among these
is the well-known memoir On the Equilibrium of Heterogeneous
Substances, which has proved to be of such fundamental importance
to Physical Chemistry and has been translated into German by
Professor Ostwald, and into French by Professor Le Chatelier.
*" Elementary Principles in Statistical Mechanics developed with especial reference
to the Rational Foundation of Thermodynamics." By J. Willard Gibbs. Charles
Scribner's Sons, New York. Edwin Arnold, London. 1902.
f " Vector Analysis, a text-book for the use of students of Mathematics and Physics,
founded upon the Lectures of J. Willard Gibbs." By E. B. Wilson. Charles Scribner's
Sons, New York. Edwin Arnold, London. 1901.
vi PEEFACE.
Shortly before the author's death he had yielded to numerous
requests for a republication of his thermodynamic papers, and had
arranged for a volume which was to contain the Equilibrium of
Heterogeneous Substances and the two earlier papers, Graphical
Methods in the Thermodynamics of Fluids, and A Method of
Geometrical Representation of the Thermodynamic Properties of
Substances by means of Surfaces. To these he proposed to add
some supplementary chapters, the preparation of which he had hardly
more than commenced when he was overtaken by his last illness.
The manuscript of a portion of this additional material (evidently
a first draft) was found among the author's papers and has been
printed at the end of the first volume. It is believed that it will
be of interest and value in spite of its unfinished and somewhat
fragmentary condition.
The remaining papers, which compose the second volume, are
divided between mathematical and physical science. Most of them
naturally fall under one of the following heads: Dynamics, Vector
Analysis and Multiple Algebra, the Electromagnetic Theory of Light,
and are so grouped in the volume in the order named. A fourth
section is made up of the unclassified papers.
In the first section the short abstract of a paper read before the
American Association for the advancement of Science is worthy of
notice as showing that the fundamental ideas and methods of the
treatise on Statistical Mechanics were well developed in the author's
mind at least seventeen years before the publication of that work. ,
The second section includes the Elements of Vector Analysis,
privately printed in 1881-1884 for the use of the author's classes,
but never published. It contains in a very condensed form all the
essential features of Professor Gibbs's system of Vector Analysis,
but without the illustrations and applications which he was accus-
tomed to give in his lectures on this subject. Copies of this pamphlet
have been for many years past practically unobtainable. Here is
also placed a hitherto unpublished letter to the editor of Klinkerfues'
Theoretische Astronomic, on the use of the author's vector method
for the determination of orbits.
Five papers on the Electromagnetic Theory of Light constitute
the third section. The fourth and last is composed of miscellaneous
papers, including biographical sketches of Clausius and of the
author's colleague Hubert A. Newton.
The editors have spared no pains to make the reprint typographi-
cally accurate. In a few cases slight corrections had been made by
Professor Gibbs in his own copies of the papers. These changes,
together with the correction, of obvious misprints in the originals,
have been incorporated in the present edition without comment.
PREFACE. vii
Where for the sake of clearness it has seemed desirable to the editors
to insert a word or two in a footnote or in the text itself, the addition
has been indicated by enclosing it within square brackets [], a sign
which is otherwise used only in the formulae.
A sketch of the life and estimate of the work of Professor Gibbs,
by one of the editors, is placed at the beginning of the first volume.
It is taken, with some additions, from the American Journal of
Science, September 1903.
HENRY ANDREWS BUMSTEAD.
RALPH GIBBS VAN NAME.
YALE UNIVERSITY,
NEW HAVEN,
October 1906.
CONTENTS OF VOLUME I.
THERMOD YNA MICS.
BIOGRAPHICAL SKETCH,
I. GRAPHICAL METHODS IN THE THERMODYNAMICS OF FLUIDS,
[Trans. Conn. Acad., vol. n, pp. 309-342, 1873.]
II. A METHOD OF GEOMETRICAL REPRESENTATION OF THE
THERMODYNAMIC PROPERTIES OF SUBSTANCES BY MEANS
OF SURFACES, -
[Trans. Conn. Acad., vol. n, pp. 382-404, 1873.]
III. ON THE EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES,
[Trans. Conn. Acad., vol. in, pp. 108-248, 1876; pp. 343-524,
1878.]
IV. ABSTRACT OF THE "EQUILIBRIUM OF HETEROGENEOUS SUB-
STANCES," -
[Amer. Jour. Sci., ser. 3, vol. xvi, pp. 441-458, 1878.]
V. ON THE VAPOR-DENSITIES OF PEROXIDE OF NITROGEN, FORMIC
ACID, ACETIC ACID, AND PERCHLORIDE OF PHOSPHORUS, -
[Amer. Jour. Sci., ser. 3, vol. xvin, pp. 277-293 and 371-387,
1879.]
VI. ON AN ALLEGED EXCEPTION TO THE SECOND LAW OF
THERMODYNAMICS,
[Science, vol. i, p. 160, 1883.]
VII. ELECTROCHEMICAL THERMODYNAMICS. Two LETTERS TO THE
SECRETARY OF THE ELECTROLYSIS COMMITTEE OF THE
BRITISH ASSOCIATION FOR THE ADVANCEMENT OF SCIENCE,
[British Association Report, 1886, pp. 388, 389 ; 1888, pp. 343-
346.]
VIII. SEMI-PERMEABLE FILMS AND OSMOTIC PRESSURE, -
[Nature, vol. LV, pp. 461, 462, 1897.]
IX. UNPUBLISHED FRAGMENTS OF A SUPPLEMENT TO THE " EQUI-
LIBRIUM OF HETEROGENOUS SUBSTANCES,"
PACK
xiii
33
55
354
372
404
406
413
418
CONTENTS OF VOLUME II.
DYNAMICS.
PAGE
I. ON THE FUNDAMENTAL FORMULAE OF DYNAMICS, 1
[Amer. Jour. Math., vol. n, pp. 49-64, 1879.]
II. ON THE FUNDAMENTAL FORMULA OF STATISTICAL MECHANICS
WITH APPLICATIONS TO ASTRONOMY AND THERMO-
DYNAMICS. (ABSTRACT), - 16
[Proc. Amer. Assoc., vol. xxxin, pp. 57, 58, 1884.]
VECTOR ANALYSIS AND MULTIPLE ALGEBRA.
III. ELEMENTS OF VECTOR ANALYSIS, ARRANGED FOR THE USE
OF STUDENTS IN PHYSICS, 17
[Not published. Printed, New Haven, pp. 1-36, 1881 ; pp.
37-83, 1884.]
IV. ON MULTIPLE ALGEBRA. VICE-PRESIDENT'S ADDRESS BEFORE
THE AMERICAN ASSOCIATION FOR THE ADVANCEMENT OF
SCIENCE, - 91
<
[Proc. Amer. Assoc., vol. xxxv, pp. 37-66, 1886.]
V. ON THE DETERMINATION OF ELLIPTIC ORBITS FROM THREE
COMPLETE OBSERVATIONS, - 118
[Mem. Nat. Acad. Sci., vol. iv, part 2, pp. 79-104, 1889.]
VI. ON THE USE OF THE VECTOR METHOD IN THE DETERMINATION
OF ORBITS. LETTER TO THE EDITOR OF KLINKERFUES'
" THEORETISCHE ASTRONOMIE," - 149
[Hitherto unpublished.]
VII. ON THE R6LE OF QUATERNIONS IN THE ALGEBRA OF VECTORS, 155
[Nature, vol. XLIII, pp. 511-513, 1891.]
VIII. QUATERNIONS AND THE " AUSDEHNUNGSLEHRE," - 161
[Nature, vol. xuv, pp. 79-82, 1891.]
IX. QUATERNIONS AND THE ALGEBRA OF VECTORS, - 169
[Nature, vol. XLVII, pp. 463, 464, 1893.]
X. QUATERNIONS AND VECTOR ANALYSIS, - 173
[Nature, vol. XLVIII, pp. 364-367, 1893.]
CONTENTS. xi
THE ELECTROMAGNETIC THEORY OF LIGHT.
PAGE
XL ON DOUBLE REFRACTION AND THE DISPERSION OF COLORS
IN PERFECTLY TRANSPARENT MEDIA, 182
[Amer. Jour. Sci., ser 3, vol. xxiu, pp. 262-275, 1882.]
XII. ON DOUBLE REFRACTION IN PERFECTLY TRANSPARENT MEDIA
WHICH EXHIBIT THE PHENOMENA OF CIRCULAR POLARIZA-
TION, - 195
[Amer. Jour. Sci., ser. 3, vol. xxm, pp. 460-476, 1882.]
XIII. ON THE GENERAL EQUATIONS OF MONOCHROMATIC LIGHT IN
MEDIA OF EVERY DEGREE OF TRANSPARENCY, 211
[Amer. Jour. Sci., ser. 3, vol. xxv, pp. 107-118, 1883.]
XIV. A COMPARISON OF THE ELASTIC AND THE ELECTRICAL
THEORIES OF LIGHT WITH RESPECT TO THE LAW OF
DOUBLE REFRACTION AND THE DISPERSION OF COLORS, - 223
[Amer. Jour. Sci., ser. 3, vol. xxxv, pp. 467-475, 1888.]
XV. A COMPARISON OF THE ELECTRIC THEORY OF LIGHT AND
SIR WILLIAM THOMSON'S THEORY OF A QUASI-LABILE
ETHER, 232
[Amer. Jour. Sci., ser. 3, vol. xxxvn, pp. 129-144, 1889.]
MISCELLANEOUS PAPERS.
XVI. REVIEWS OF NEWCOMB AND MICHELSON'S "VELOCITY OF
LIGHT IN AIR AND REFRACTING MEDIA" AND OF
KETTELER'S " THEORETISCHE OPTIK," 247
[Amer. Jour. Sci., ser. 3, vol. xxxi, pp. 62-67, 1886.]
XVII. ON THE VELOCITY OF LIGHT AS DETERMINED BY FOUCAULT'S
REVOLVING MIRROR, - 253
[Nature, vol. xxxui, p. 582, 1886.]
XVIII. VELOCITY OF PROPAGATION OF ELECTROSTATIC FORCE, 255
[Nature, vol. LIII, p. 509, 1896.]
XIX. FOURIER'S SERIES, 258
[Nature, vol. LIX, pp. 200 and 606, 1898-99.]
XX. RUDOLF JULIUS EMANUEL CLAUSIUS, - 261
[Proc. Amer. Acad., new series, vol. xvi, pp. 458-465, 1889.]
XXI. HUBERT ANSON NEWTON, - 268
[Amer. Jour. Sci., ser. 4, vol. ill, pp. 359-376, 1897.]
JOSIAH WILLARD GIBBS.
[Reprinted with some additions from the American Journal of Science,
ser. 4, vol. xvi., September, 1903.]
JOSIAH WILLARD GIBBS was born in New Haven, Connecticut,
February 11, 1839, and died in the same city, April 28, 1903. He
was descended from Robert Gibbs, the fourth son of Sir Henry Gibbs
of Honington, Warwickshire, who came to Boston about 1658. One of
Robert Gibbs's grandsons, Henry Gibbs, in 1747 married Katherine,
daughter of the Hon. Josiah Willard, Secretary of the Province of
Massachusetts, and of the descendants of this couple, in various parts
of the country, no fewer than six have borne the name Josiah Willard
Gibbs.
The subject of this memorial was the fourth child and only son of
Josiah Willard Gibbs, Professor of Sacred Literature in the Yale
Divinity School from 1824 to 1861, and of his wife, Mary Anna,
daughter of Dr. John Van Cleve of Princeton, N.J. The elder
Professor Gibbs was remarkable among his contemporaries for pro-
found scholarship, for unusual modesty, and for the conscientious and
painstaking accuracy which characterized all of his published work.
The following brief extracts from a discourse commemorative of his
life, by Professor George P. Fisher, can hardly fail to be of interest to
those who are familiar with the work of his distinguished son : " One
who should look simply at the writings of Mr. Gibbs, where we meet
only with naked, laboriously classified, skeleton-like statements of
scientific truth, might judge him to be devoid of zeal even in his
favorite pursuit. But there was a deep fountain of feeling that did
not appear in these curiously elaborated essays. ... Of the science
of comparative grammar, as I am informed by those most competent
to judge, he is to be considered in relation to the scholars of this
country as the leader/' Again, in speaking of his unfinished trans-
lation of Gesenius's Hebrew Lexicon : " But with his wonted
thoroughness, he could not leave a word until he had made the article
upon it perfect, sifting what the author had written by independent
investigations of his own."
The ancestry of the son presents other points of interest. On his
G.I. b
xiv JOSIAH WILLARD GIBBS.
father's side we find an unbroken line of six college graduates. Five
of these were graduates of Harvard, — President Samuel Willard, his
son Josiah Willard, the great grandfather, grandfather and father of
the elder Professor Gibbs, who was himself a graduate of Yale.
Among his mother's ancestors were two more Yale graduates, one of
whom, Rev. Jonathan Dickinson, was the first President of the College
of New Jersey.
Josiah Willard Gibbs, the younger, entered Yale College in 1854
and was graduated in 1858, receiving during his college course several
prizes for excellence in Latin and Mathematics ; during the next five
years he continued his studies in New Haven, and in 1863 received
the degree of doctor of philosophy and was appointed a tutor in the
college for a term of three years. During the first two years of his
tutorship he taught Latin and in the third year Natural Philosophy,
in both of which subjects he had gained marked distinction as an
undergraduate. At the end of his term as tutor he went abroad with
his sisters, spending the winter of 1866-67 in Paris and the following
year in Berlin, where he heard the lectures of Magnus and other
teachers of physics and of mathematics. In 1868 he went to Heidel-
berg, where Kirchhoff and Helmholtz were then stationed, returning
to New Haven in June, 1869. Two years later he was appointed
Professor of Mathematical Physics in Yale College, a position which
he held until the time of his death.
It was not until 1873, when he was thirty-four years old, that he
gave to the world, by publication, evidence of his extraordinary
powers as an investigator in mathematical physics. In that year two
papers appeared in the Transactions of the Connecticut Academy, the
first being entitled " Graphical Methods in the Thermodynamics of
Fluids," and the second " A Method of Geometrical Representation of
the Thermodynamic Properties of Substances by Means of Surfaces."
These were followed in 1876 and 1878 by the two parts of the great
paper " On the Equilibrium of Heterogeneous Substances," which is
generally, and probably rightly, considered his most important contri-
bution to physical science, and which is unquestionably among the
greatest and most enduring monuments of the wonderful scientific
activity of the nineteenth century. The first two papers of this series,
although somewhat overshadowed by the third, are themselves very
remarkable and valuable contributions to the theory of thermo-
dynamics ; they have proved useful and fertile in many direct ways,
and, in addition, it is difficult to see how, without them, the third
could have been written. In logical development the three are very
closely connected, and methods first brought forward in the earlier
papers are used continually in the third.
Professor Gibbs was much inclined to the use of geometrical
JOSIAH WILLARD GIBBS. xv
illustrations, which he employed as symbols and aids to the imagin-
ation, rather than the mechanical models which have served so many
great investigators ; such models are seldom in complete correspondence
with the phenomena they represent, and Professor Gibbs's tendency
toward rigorous logic was such that the discrepancies apparently
destroyed for him the usefulness of the model. Accordingly he usually
had recourse to the geometrical representation of his equations, and
this method he used with great ease and power. With this inclination,
it is probable that he made much use, in his study of thermodynamics,
of the volume-pressure diagram, the only one which, up to that time,
had been used extensively. To those who are acquainted with the
completeness of his investigation of any subject which interested him,
it is not surprising that his first published paper should have been a
careful study of all the different diagrams which seemed to have any
chance of being useful. Of the new diagrams which he first described
in this paper, the simplest, in some respects, is that in which entropy
and temperature are taken as coordinates ; in this, as in the familiar
volume-pressure diagram, the work or heat of any cycle is proportional
to its area in any part of the plane ; for many purposes it is far more
perspicuous than the older diagram, and it has found most important
practical applications in the study of the steam engine. The diagram,
however, to which Professor Gibbs gave most attention was the
volume-entropy diagram, which presents many advantages when the
properties of bodies are to be studied, rather than the work they do or
the heat they give out. The chief reason for this superiority is that
volume and entropy are both proportional to the quantity of substance,
while pressure and temperature are not ; the representation of coexis-
tent states is thus especially clear, and for many purposes the gain in
this direction more than counter-balances the loss due to the variability
of the scale of work and heat. No diagram of constant scale can, for
example, adequately represent the triple state where solid, liquid and
vapor are all present; nor, without confusion, can it represent the
states of a substance which, like water, has a maximum density; in
these and in many other cases the volume-entropy diagram is superior
in distinctness and convenience.
In the second paper the consideration of graphical methods in
thermodynamics was extended to diagrams in three dimensions.
James Thomson had already made this extension to the volume-pressure
diagram by erecting the temperature as the third coordinate, these
three immediately cognizable quantities giving a surface whose inter-
pretation is most simple from elementary considerations, but which,
for several reasons, is far less convenient and fertile of results than
one in which the coordinates are thermodynamic quantities less directly
known. In fact, if the general relation between the volume, entropy
xvi JOSIAH WILLARD GIBBS.
and energy of any body is known, the relation between the volume,
pressure and temperature may be immediately deduced by differen-
tiation ; but the converse is not true, and thus a knowledge of the
former relation gives more complete information of the properties of a
substance than a knowledge of the latter. Accordingly Gibbs chooses
as the three coordinates the volume, entropy and energy and, in a
masterly manner, proceeds to develop the properties of the resulting
surface, the geometrical conditions for equilibrium, the criteria for its
stability or instability, the conditions for coexistent states and for the
critical state ; and he points out, in several examples, the great power
of this method for the solution of thermodynamic problems. The
exceptional importance and beauty of this work by a hitherto unknown
writer was immediately recognized by Maxwell, who, in the last years
of his life, spent considerable time in carefully constructing, with his
own hands, a model of this surface, a cast of which, very shortly before
his death, he sent to Professor Gibbs.
One property of this three dimensional diagram (analogous to that
mentioned in the case of the plane volume-entropy diagram) proved
to be of capital importance in the development of Gibbs's future work
in thermodynamics ; the volume, entropy and energy of a mixture of
portions of a substance in different states (whether in equilibrium or
not), are the sums of the volumes, entropies and energies of the separate
parts, and, in the diagram, the mixture is represented by a single point
which may be found from the separate points, representing the different
portions, by a process like that of finding centers of gravity. In
general this point is not in the surface representing the stable States
of the substance, but within the solid bounded by this surface, and
its distance from the surface, taken parallel to the axis of energy,
represents the available energy of the mixture. This possibility of
representing the properties of mixtures of different states of the same
substance immediately suggested that mixtures of substances differing
in chemical composition, as well as in physical state, might be treated
in a similar manner; in a note at the end of the second paper the
author clearly indicates the possibility of doing so, and there can be
little doubt that this was the path by which he approached the task
of investigating the conditions of chemical equilibrium, a task which
he was destined to achieve in such a magnificent manner and with
such advantage to physical science.
In the discussion of chemically homogeneous substances in the first
two papers, frequent use had been made of the principle that such a
substance will be in equilibrium if, when its energy is kept constant,
its entropy cannot increase ; at the head of the third paper the author
puts the famous statement of Clausius : " Die Energie der Welt ist
constant. Die Entropie der Welt strebt einem Maximum zu." He
JOSIAH WILLARD GIBBS. xvii
proceeds to show that the above condition for equilibrium, derived
from the two laws of thermodynamics, is of universal application,
carefully removing one restriction after another, the first to go being
that the substance shall be chemically homogeneous. The important
analytical step is taken of introducing as variables in the fundamental
differential equation, the masses of the constituents of the hetero-
geneous body; the differential coefficients of the energy with respect
to these masses are shown to enter the conditions of equilibrium in a
manner entirely analogous to the "intensities," pressure and temper-
ature, and these coefficients are called potentials. Constant use is
made of the analogies with the equations for homogeneous substances,
and the analytical processes are like those which a geometer would
use in extending to n dimensions the geometry of three.
It is quite out of the question to give, in brief compass, anything
approaching an adequate outline of this remarkable work. It is
universally recognized that its publication was an event of the first
importance in the history of chemistry, that in fact it founded a new
department of chemical science which, in the words of M. Le Chatelier,
is becoming comparable in importance with that created by Lavoisier.
Nevertheless it was a number of years before its value was generally
known ; this delay was due largely to the fact that its mathematical
form and rigorous deductive processes make it difficult reading for
any one, and especially so for students of experimental chemistry
whom it most concerns; twenty-five years ago there was relatively
only a small number of chemists who possessed sufficient mathematical
knowledge to read easily even the simpler portions of the paper.
Thus it came about that a number of natural laws of great importance
which were, for the first time, clearly stated in this paper were subse-
quently, during its period of neglect, discovered by others, sometimes
from theoretical considerations, but more often by experiment. At
the present time, however, the great value of its methods and results
are fully recognized by all students of physical chemistry. It was
translated into German in 1891 by Professor Ostwald and into French
in 1899 by Professor Le Chatelier ; and, although so many years had
passed since its original publication, in both cases the distinguished
translators give, as their principal reason for undertaking the task,
not the historical interest of the memoir, but the many important
questions which it discusses and which have not even yet been worked
out experimentally. Many of its theorems have already served as
starting points or guides for experimental researches of fundamental
consequence; others, such as that which goes under the name of
the "Phase Rule," have served to classify and explain, in a simple
and logical manner, experimental facts of much apparent complexity ;
while still others, such as the theories of catalysis, of solid solutions,
xviii JOSIAH WILLARD GIBBS.
and of the action of semi-permeable diaphragms and osmotic pressure,
showed that many facts, which had previously seemed mysterious and
scarcely capable of explanation, are in fact simple, direct and necessary
consequences of the fundamental laws of thermodynamics. In the
discussion of mixtures in which some of the components are present
only in very small quantity (of which the most interesting cases at
present are dilute solutions) the theory is carried as far as is possible
from d priori considerations ; at the time the paper was written the
lack of experimental facts did not permit the statement, in all its
generality, of the celebrated law which was afterward discovered by
van't Hoff ; but the law is distinctly stated for solutions of gases as a
direct consequence of Henry's law and, while the facts at the author's
disposal did not permit a further extension, he remarks that there are
many indications " that the law expressed by these equations has a
very general application."
It is not surprising that a work containing results of such conse-
quence should have excited the prof oundest admiration among students
of the physical sciences ; but even more remarkable than the results,
and perhaps of even greater service to science, are the methods by
which they were attained ; these do not depend upon special hypotheses
as to the constitution of matter or any similar assumption, but the
whole system rests directly upon the truth of certain experiential
laws which possess a very high degree of probability. To have
obtained the results embodied in these papers- in any manner would
have been a great achievement ; that they were reached by a method
of such logical austerity is a still greater cause for wonder and
admiration. And it gives to the work a degree of certainty and an
assurance of permanence, in form and matter, which is not often
found in investigations so original in character.
In lecturing to students upon mathematical physics, especially in
the theory of electricity and magnetism, Professor Gibbs felt, as so
many other physicists in recent years have done, the desirability of a
vector algebra by which the more or less complicated space relations,
dealt with in many departments of physics, could be conveniently and
perspicuously expressed ; and this desire was especially active in him
on account of his natural tendency toward elegance and conciseness
of mathematical method. He did not, however, find in Hamilton's
system of quaternions an instrument altogether suited to his needs,
in this respect sharing the experience of other investigators who have,
of late years, seemed more and more inclined, for practical purposes,
to reject the quaternionic analysis, notwithstanding its beauty and
logical completeness, in favor of a simpler and more direct treatment
of the subject. For the use of his students, Professor Gibbs privately
JOSIAH WILLAKD GIBBS. xix
printed in 1881 and 1884 a very concise account of the vector analysis
which he had developed, and this pamphlet was to some extent circu-
lated among those especially interested in the subject. In the develop-
ment of this system the author had been led to study deeply the
Ausdehnungslehre of Grassmann, and the subject of multiple algebra
in general ; these investigations interested him greatly up to the time
of his death, and he has often remarked that he had more pleasure in
the study of multiple algebra than in any other of his intellectual
activities. His rejection of quaternions, and his championship of
Grassmann's claim to be considered the founder of modern algebra,
led to some papers of a somewhat controversial character, most of
which appeared in the columns of Natwre. When the utility of
his system as an instrument for physical research had been proved
by twenty years' experience of himself and of his pupils, Professor
Gibbs consented, though somewhat reluctantly, to its formal publi-
cation in much more extended form than in the original pamphlet.
As he was at that time wholly occupied with another work, the task
of preparing this treatise for publication was entrusted to one of his
students, Dr. E. B. Wilson, whose very successful accomplishment of
the work entitles him to the gratitude of all who are interested in
the subject.
The reluctance of Professor Gibbs to publish his system of vector
analysis certainly did not arise from any doubt in his own mind as
to its utility, or the desirability of its being more widely employed ;
it seemed rather to be due to the feeling that it was not an original
contribution to mathematics, but was rather an adaptation, for special
purposes, of the work of others. Of many portions of the work this
is of course necessarily true, and it is rather by the selection of
methods and by systematization of the presentation that the author
has served the cause of vector analysis. But in the treatment of the
linear vector function and the theory of dyadics to which this leads,
a distinct advance was made which was of consequence not only in
the more restricted field of vector analysis, but also in the broader
theory of multiple algebra in general.
The theory of dyadics* as developed in the vector analysis of 1884
must be regarded as the most important published contribution of
Professor Gibbs to pure mathematics. For the vector analysis as an
algebra does not fulfil the definition of the linear associative algebras
of Benjamin Peirce, since the scalar product of vectors lies outside the
vector domain; nor is it a geometrical analysis in the sense of
* The three succeeding paragraphs are by Professor Percey F. Smith ; they form part
of a sketch of Professor Gibbs's work in pure mathematics, which Professor Smith con-
tributed to the Bulletin of the, American Mathematical Society, vol. x, p. 34 (October,
1903).
xx JOSIAH WILLARD GIBBS.
Grassmann, the vector product satisfying the combinatorial law, but
yielding a vector instead of a magnitude of the second order. While
these departures from the systems mentioned testify to the great
ingenuity and originality of the author, and do not impair the utility
of the system as a tool for the use of students of physics, they never-
theless expose the discipline to the criticism of the pure algebraist.
Such objection falls to the ground, however, in the case of the theory
mentioned, for dyadics yield, for n = 3, a linear associative algebra of
nine units, namely nonions, the general nonion satisfying an identical
equation of the third degree, the Hamilton-Cayley equation.
It is easy to make clear the precise point of view adopted by
Professor Gibbs in this matter. This is well expounded in his vice-
presidential address on multiple algebra, before the American Asso-
ciation for the Advancement of Science, in 1886, and also in his warm
defense of Grassmann's priority rights, as against Hamilton's, in his
article in Nature "Quaternions and the Ausdehnungslehre." He
points out that the key to matricular algebras is to be found in the
open (or indeterminate) product (i.e., a product in which no equations
subsist between the factors), and, after calling attention to the brief
development of this product in Grassmann's work of 1844, affirms
that Sylvester's assignment of the date 1858 to the " second birth of
Algebra" (this being the year of Cayley's Memoir on Matrices) must be
changed to 1844. Grassmann, however, ascribes very little importance
to the open product, regarding it as offering no useful applications.
On the contrary, Professor Gibbs assigns to it the first place in the
three kinds of multiplication considered in the Ausdehnungsfahre,
since from it may be derived the algebraic and the combinatorial
products, and shows in fact that both of them may be expressed in
terms of indeterminate products. Thus the multiplication rejected
by Grassmann becomes, from the standpoint of Professor Gibbs, the
key to all others. The originality of the latter's treatment of the
algebra of dyadics, as contrasted with the methods of other authors in
the allied theory of matrices, consists exactly in this, that Professor
Gibbs regards a matrix of order n as a multiple quantity in n2 units,
each of which is an indeterminate product of two factors. On the
other hand, C. S. Peirce, who was the first to recognize (1870) the
quadrate linear associative algebras identical with matrices, uses for
the units a letter pair, but does not regard this combination as a
product. In addition, Professor Gibbs, following the spirit of
Grassmann's system, does not confine himself to one kind of multi-
plication of dyadics, as do Hamilton and Peirce, but considers two
sorts, both originating with Grassmann. Thus it may be said that
quadrate, or matricular algebras, are brought entirely within the
wonderful system expounded by Grassmann in 1844.
JOSIAH WILLARD GIBBS. xxi
As already remarked, the exposition of the theory of dyadics given
in the vector analysis is not in accord with Grassmann's system. In
a footnote to the address referred to above, Professor Gibbs shows the
slight modification necessary for this purpose, while the subject has
been treated in detail and in all generality in his lectures on multiple
algebra delivered for some years past at Yale University.
Professor Gibbs was much interested in the application of vector
analysis to some of the problems of astronomy, and gave examples
of such application in a paper, " On the Determination of Elliptic
Orbits from Three Complete Observations" (Mem. Nat. Acad. Sci.,
vol. iv, pt. 2, pp. 79-104). The methods developed in this paper were
afterwards applied by Professors W. Beebe and A. W. Phillips* to
the computation of the orbit of Swift's comet (1880 V) from three
observations, which gave a very critical test of the method. They
found that Gibbs's method possessed distinct advantages over those
of Gauss and Oppolzer; the convergence of the successive approxi-
mations was more rapid and the labor of preparing the fundamental
equations for solution much less. These two papers were translated
by Buchholz and incorporated in the second edition of Klinkerfues'
Theoretische Astronomie.
Between the years 1882 and 1889, five papers appeared in The
American Journal of Science upon certain points in the electro-
magnetic theory of light and its relations to the various elastic
theories. These are remarkable for the entire absence of special
hypotheses as to the connection between ether and matter, the
only supposition made as to the constitution of matter being that
it is fine-grained with reference to the wave-length of light, but
not infinitely fine-grained, and that it does disturb in some manner
the electrical fluxes in the ether. By methods whose simplicity
and directness recall his thermodynamic investigations, the author
shows in the first of these articles that, in the case of perfectly
transparent media, the theory not only accounts for the dispersion
of colors (including the "dispersion of the optic axes" in doubly
refracting media), but also leads to Fresnel's laws of double refrac-
tion for any particular wave-length without neglect of the small
quantities which determine the dispersion of colors. He proceeds
in the second paper to show that circular and elliptical polariza-
tion are explained by taking into account quantities of a still
higher order, and that these in turn do not disturb the explanation
of any of the other known phenomena; and in the third paper he
deduces, in a very rigorous manner, the general equations of mono-
chromatic light in media of every degree of transparency, arriving
* Astronomical Journal, vol. ix, pp. 114-117, 121-124, 1889.
xxii JOSIAH WILLABD GIBBS.
at equations somewhat different from those of Maxwell in that they
do not contain explicitly the dielectric constant and conductivity as
measured electrically, thus avoiding certain difficulties (especially in
regard to metallic reflection) which the theory as originally stated had
encountered ; and it is made clear that " a point of view more in
accordance with what we know of the molecular constitution of
bodies will give that part of the ordinary theory which is verified
by experiment, without including that part which is in opposition
to observed facts." Some experiments of Professor C. S. Hastings
in 1888 (which showed that the double refraction in Iceland spar
conformed to Huyghens's law to a degree of precision far exceeding
that of any previous verification) again led Professor Gibbs to take
up the subject of optical theories in a paper which shows, in a
remarkably simple manner, from elementary considerations, that this
result and also the general character of the facts of dispersion are in
strict accord with the electrical theory, while no one of the elastic
theories which had, at that time, been proposed could be reconciled
with these experimental results. A few months later upon the publi-
cation of Sir William Thomson's theory of an infinitely compressible
ether, it became necessary to supplement the comparison by taking
account of this theory also. It is not subject to the insuperable
difficulties which beset the other elastic theories, since its equations
and surface conditions for perfectly homogeneous and transparent
media are identical in form with those of the electrical theory, and
lead in an equally direct manner to Fresnel's construction for doubly-
refracting media, and to the proper values for the intensities of the
reflected and refracted light. But Gibbs shows that, in the case of
a fine-grained medium, Thomson's theory does not lead to the known
facts of dispersion without unnatural and forced hypotheses, and that
in the case of metallic reflection it is subject to similar difficulties;
while, on the other hand, "it may be said for the electrical theory
that it is not obliged to invent hypotheses, but only to apply the
laws furnished by the science of electricity, and that it is difficult to
account for the coincidences between the electrical and optical pro-
perties of media unless we regard the motions of light as electrical."
Of all the arguments (from theoretical- grounds alone) for excluding
all other theories of light except the electrical, these papers furnish
the simplest, most philosophical, and most conclusive with which the
present writer is acquainted; and it seems likely that the con-
siderations advanced in them would have sufficed to firmly establish
this theory even if the experimental discoveries of Hertz had not
supplied a more direct proof of its validity.
In his last work, Elementary Principles in Statistical Mechanics,
JOSIAH WILLARD GIBBS. xxiii
Professor Gibbs returned to a theme closely connected with the
subjects of his earliest publications. In these he had been concerned
with the development of the consequences of the laws of thermo-
dynamics which are accepted as given by experience ; in this empirical
form of the science, heat and mechanical energy are regarded as two
distinct entities, mutually convertible of course with certain limita-
tions, but essentially different in many important ways. In accordance
with the strong tendency toward unification of causes, there have been
many attempts to bring these two things under the same category;
to show, in fact, that heat is nothing more than the purely mechanical
energy of the minute particles of which all sensible matter is supposed
to be made up, and that the extra-dynamical laws of heat are con-
sequences of the immense number of independent mechanical systems
in any body, — a number so great that, to human observation, only
certain averages and most probable effects are perceptible. Yet in
spite of dogmatic assertions, in many elementary books and popular
expositions, that " heat is a mode of molecular motion," these attempts
have not been entirely successful, and the failure has been signalized
by Lord Kelvin as one of the clouds upon the history of science in
the nineteenth century. Such investigations must deal with the
mechanics of systems of an immense number of degrees of freedom
and (since we are quite unable in our experiments to identify or
follow individual particles), in order to compare the results of the
dynamical reasoning with observation, the processes must be statistical
in character. The difficulties of such processes have been pointed out
more than once by Maxwell, who, in a passage which Professor Gibbs
often quoted, says that serious errors have been made in such inquiries
by men whose competency in other branches of mathematics was un-
questioned.
On account, then, of the difficulties of the subject and of the pro-
found importance of results which can be reached by no other known
method, it is of the utmost consequence that the principles and pro-
cesses of statistical mechanics should be put upon a firm and certain
foundation. That this has now been accomplished there can be no
doubt, and there will be little excuse in the future for a repetition of
the errors of which Maxwell speaks ; moreover, theorems have been
discovered and processes devised which will render easier the task of
every future student of this subject, as the work of Lagrange did in
the case of ordinary mechanics.
The greater part of the book is taken up with this general develop-
ment of the subject without special reference to the problems of
rational thermodynamics. At the end of the twelfth chapter the
author has in his hands a far more perfect weapon for attacking such
problems than any previous investigator has possessed, and its
xxiv JOSIAH WILLARD GIBBS.
triumphant use in the last three chapters shows that such purely
mechanical systems as he has been considering will exhibit, to human
perception, properties in all respects analogous to those which we
actually meet with in thermodynamics. No one can understandingly
read the thirteenth chapter without the keenest delight, as one after
another of the familar formulae of thermodynamics appear almost
spontaneously, as it seems, from the consideration of purely mechanical
systems. But it is characteristic of the author that he should be more
impressed with the limitations and imperfections of his work than
with its successes ; and he is careful to say (p. 166) : " But it should be
distinctly stated, that if the results obtained when the numbers of
degrees of freedom are enormous coincide sensibly with the general
laws of thermodynamics, however interesting and significant this
coincidence may be, we are still far from having explained the
phenomena of nature with respect to these laws. For, as compared
with the case of nature, the systems which we have considered are of
an ideal simplicity. Although our only assumption is that we are
considering conservative systems of a finite number of degrees of
freedom, it would seem that this is assuming far too much, so far as
the bodies of nature are concerned. The phenomena of radiant heat,
which certainly should not be neglected in any complete system of
thermodynamics, and the electrical phenomena associated with the
combination of atoms, seem to show that the hypothesis of a finite
number of degrees of freedom is inadequate for the explanation of the
properties of bodies." While this is undoubtedly true, it should, also
be remembered that, in no department of physics have the phe-
nomena of nature been explained with the completeness that is here
indicated as desirable. In the theories of electricity, of light, even in
mechanics itself, only certain phenomena are considered which really
never occur alone. In the present state of knowledge, such partial
explanations are the best that can be got, and, in addition, the
problem of rational thermodynamics has, historically, always been
regarded in this way. In a matter of such difficulty no positive
statement should be made, but it is the belief of the present
writer that the problem, as it has always been understood, has been
successfully solved in this work ; and if this belief is correct, one of
the great deficiencies in the scientific record of the nineteenth century
has been supplied in the first year of the twentieth.
In methods and results, this part of the work is more general than
any preceding treatment of the subject ; it is in no sense a treatise on
the kinetic theory of gases, and the results obtained are not the
properties of any one form of matter, but the general equations of
thermodynamics which belong to all forms alike. This corresponds to
the generality of the hypothesis in which nothing is assumed as to
JOSIAH WILLARD GIBBS. xxv
the mechanical nature of the systems considered, except that they are
mechanical and obey Lagrange's or Hamilton's equations. In this
respect it may be considered to have done for thermodynamics what
Maxwell's treatise did for electromagnetism, and we may say (as
Poincare has said of Maxwell) that Gibbs has not sought to give a
mechanical explanation of heat, but has limited his task to de-
monstrating that such an explanation is possible. And this achieve-
ment forms a fitting culmination of his life's work.
The value to science of Professor Gibbs's work has been formally
recognized by many learned societies and universities both in this
country and abroad. The list of societies and academies of which he
was a member or correspondent includes the Connecticut Academy of
Arts and Sciences, the National Academy of Sciences, the American
Academy of Arts and Sciences, the American Philosophical Society,
the Dutch Society of Sciences, Haarlem, the Royal Society of Sciences,
Gottingen, the Royal Institution of Great Britain, the Cambridge
Philosophical Society, the London Mathematical Society, the Man-
chester Literary and Philosophical Society, the Royal Academy of
Amsterdam, the Royal Society of London, the Royal Prussian
Academy of Berlin, the French Institute, the Physical Society of
London, and the Bavarian Academy of Sciences. He was the
recipient of honorary degrees from Williams College, and from the
universities of Erlangen, Princeton, and Christiania. In 1881 he
received the Rumford Medal from the American Academy of Boston,
and in 1901 the Copley Medal from the Royal Society of London.
Outside of his scientific activities, Professor Gibbs's life was
uneventful ; he made but one visit to Europe, and with the exception
of those three years, and of summer vacations in the mountains, his
whole life was spent in New Haven, and all but his earlier years in
the same house, which his father had built only a few rods from the
school where he prepared for college and from the university in the
service of which his life was spent. His constitution was never
robust — the consequence apparently of an attack of scarlet fever in
early childhood — but with careful attention to health and a regular
mode of life his work suffered from this cause no long or serious
interruption until the end, which came suddenly after an illness of
only a few days. He never married, but made his home with his
sister and her family. Of a retiring disposition, he went little into
general society and was known to few outside the university ; but
by those who were honoured by his friendship, and by his students,
he was greatly beloved. His modesty with regard to his work was
proverbial among all who knew him, and it was entirely real and
unaffected. There was never any doubt in his mind, however, as
xxvi JOSIAH WILLARD GIBBS.
to the accuracy of anything which he published, nor indeed did he
underestimate its importance; but he seemed to regard it in an
entirely impersonal way and never doubted, apparently, that what he
had accomplished could have been done equally well by almost anyone
who might have happened to give his attention to the same problems.
Those nearest him for many years are constrained to believe that he
never realized that he was endowed with most unusual powers of
mind ; there was never any tendency to make the importance of his
work an excuse for neglecting even the most trivial of his duties as
an officer of the college, and he was never too busy to devote, at once,
as much time and energy as might be necessary to any of his students
who privately sought his assistance.
Although long intervals sometimes elapsed between his publications
his habits of work were steady and systematic ; but he worked alone
and, apparently, without need of the stimulus of personal conversation
upon the subject, or of criticism from others, which is often helpful
even when the critic is intellectually an inferior. So far from pub-
lishing partial results, he seldom, if ever, spoke of what he was doing
until it was practically in its final and complete form. This was his
chief limitation as a teacher of advanced students; he did not take
them into his confidence with regard to his current work, and even
when he lectured upon a subject in advance of its publication (as was
the case for a number of years before the appearance of the Statistical
Mechanics) the work was really complete except for a few finishing
touches. Thus his students were deprived of the advantage of seeing
his great structures in process of building, of helping him in4 the
details, and of being in such ways encouraged to make for themselves
attempts similar in character, however small their scale. But on the
other hand, they owe to him a debt of gratitude for an introduction
into the profounder regions of natural philosophy such as they could
have obtained from few other living teachers. Always carefully
prepared, his lectures were marked by the same great qualities as his
published papers and were, in addition, enriched by many apt and
simple illustrations which can never be forgotten by those who heard
them. No necessary qualification to a statement was ever omitted,
and, on the other hand, it seldom failed to receive the most general
application of which it was capable ; his students had ample oppor-
tunity to learn what may be regarded as known, what is guessed
at, what a proof is, and how far it goes. Although he disregarded
many of the shibboleths of the mathematical rigorists, his logical
processes were really of the most severe type ; in power of deduction,
of generalization, in insight into hidden relations, in critical acumen,
utter lack of prejudice, and in the philosophical breadth of his view
of the object and aim of physics, he has had few superiors in the
JOSIAH WILLARD GIBBS. xxvii
history of the science; and no student could come in contact with
this serene and impartial mind without feeling profoundly its influence
in all his future studies of nature.
In his personal character the same great qualities were apparent.
Unassuming in manner, genial and kindly in his intercourse with his
fellow-men, never showing impatience or irritation, devoid of personal
ambition of the baser sort or of the slightest desire to exalt himself,
he went far toward realizing the ideal of the unselfish, Christian
gentleman. In the minds of those who knew him, the greatness of
his intellectual achievements will never overshadow the beauty and
dignity of his life.
H. A. BUMSTEAD.
Bibliography.
1873. Graphical methods in the thermodynamics of fluids. Trans. Conn. Acad., vol. ii,
pp. 309-342.
A method of geometrical representation of the thermodynamic properties of
substances by means of surfaces. Ibid. , pp. 382-404.
1875-1878. On the equilibrium of heterogeneous substances. Ibid., vol. iii,
pp. 108-248 ; pp. 343-524. Abstract, Amer. Jour. Sci. (3), vol. xvi, pp. 441-458.
(A German translation of the three preceding papers by W. Ostwald has been
published under the title, " Thermodynamische Studien," Leipzig, 1892; also a.
French translation of the first two papers by G. Roy, with an introduction by
B. Brunhes, under the title " Diagrammes et surfaces therm odynamiques,"
Paris, 1903, and of the first part of the Equilibrium of Heterogeneous Substances
by H. Le Chatelier under the title "Equilibre des Systemes Chimiques," Paris,
1899.)
1879. On the fundamental formulae of dynamics. Amer. Jour. Math., vol. ii,
pp. 49-64.
On the vapor-densities of peroxide of nitrogen, formic acid, acetic acid, and
perchloride of phosphorus. Amer. -Jour. Sci. (3), vol. xviii, pp. 277-293;
pp. 371-387.
1881 and 1884. Elements of vector analysis arranged for the use of students in physics.
New Haven, 8°, pp. 1-36 in 1881, and pp. 37-83 in 1884. (Not published.)
1882-1883. Notes on the electromagnetic theory of light. I. On double refraction and
the dispersion of colors in perfectly transparent media. Amer. Jour. Sci. (3),
vol. xxiii, pp. 262-275. II. On double refraction in perfectly transparent media
which exhibit the phenomena of circular polarization. Ibid., pp. 460-476.
III. On the general equations of monochromatic light in media of every degree of
transparency. Ibid., vol. xxv, pp. 107-118.
1883. On an alleged exception to the second law of thermodynamics. Science, vol. i,
p. 160.
1884. On the fundamental formula of statistical mechanics, with applications to
astronomy and thermodynamics. (Abstract.) Proc. Amer. Assoc. Adv. Sci.,
vol. xxxiii, pp. 57, 58.
1886. Notices of Newcomb and Michelson's "Velocity of light in air and refracting
media" and of Ketteler's " Theoretische Optik." Amer. Jour. Sci. (3), vol. xxxi,
pp. 62-67.
On the velocity of light as determined by Foucault's revolving mirror.
Nature, vol. xxxiii, p. 582.
On multiple algebra. (Vice-president's address before the section of mathematics
and astronomy of the American Association for the Advancement of Science.)
Proc. Amer. Assoc. Adv. Sci., vol. xxxv, pp. 37-66.
xxviii JOSIAH WILLARD GIBBS.
1887 and 1889. Electro-chemical thermodynamics. (Two letters to the secretary of the
electrolysis committee of the British Association.) Rep. Brit. Assoc. Adv. Sci.
for 1886, pp. 388-389, and for 1888, pp. 343-346.
1888. A comparison of the elastic and electrical theories of light, with respect to the
law of double refraction and the dispersion of colors. Amer. Jour. Sci. (3),
vol. xxxv, pp. 467-475.
1889. A comparison of the electric theory of light and Sir William Thomson's theory
of a quasi-labile ether. Amer. Jour. Set., vol. xxxvii, pp. 129-144.
Reprint, Phil. Mag. (5), vol. xxvii, pp. 238-253.
On the determination of elliptic orbits from three complete observations.
Mem. Nat. Acad. Sci., vol. iv, pt. 2, pp. 79-104.
Rudolf Julius Emanuel Clausius. Proc. Amer. Acad., new series, vol. xvi,
pp. 458-465.
1891. On the r61e of quaternions in the algebra of vectors. Nature, vol. xliii, pp. 511-513.
Quaternions and the Ausdehnungslehre. Nature, vol. xliv, pp. 79-82.
1893. Quaternions and the algebra of vectors. Nature, vol. xlvii, pp. 463, 464.
1893. Quaternions and vector analysis. Nature, vol. xlviii, pp. 364-367.
1896. Velocity of propagation of electrostatic force. Nature, vol. liii, p. 509.
1897. Semi-permeable films and osmotic pressure. Nature, vol. Iv, pp. 461, 462.
Hubert Anson Newton. Amer. Jour. Sci. (4), vol. iii, pp. 359-376.
1898-99. Fourier's series. Nature, vol. lix, pp. 200, 606.
1901. Vector analysis, a text book for the use of students of mathematics and physics,
founded upon the lectures of J. Willard Gibbs, by E. B. Wilson. Pp. xviii + 436.
Yale Bicentennial Publications. C. Scribner's Sons.
1902. Elementary principles in statistical mechanics developed with especial reference
to the rational foundation of thermodynamics. Pp. xviii + 207. Yale Bi-
centennial Publications. C. Scribner's Sons.
1906. Unpublished fragments of a supplement to the "Equilibrium of Heterogeneous
Substances." Scientific Papers, vol. i, pp. 418-434.
On the use of the vector method in the determination of orbits. Letter to
Dr. Hugo Buchholz, editor of Klinkerfues' Theoretische Astronomic. Scientific
Papers, vol. ii, pp. 149-154.
I.
GRAPHICAL METHODS IN THE THERMODYNAMICS
OF FLUIDS.
[Transactions of the Connecticut Academy, II., pp. 309-342, April-May, 1873.]
ALTHOUGH geometrical representations of propositions in the thermo-
dynamics of fluids are in general use, and have done good service
in disseminating clear notions in this science, yet they have by no
means received the extension in respect to variety and generality
of which they are capable. So far as regards a general graphical
method, which can exhibit at once all the thermodynamic properties
of a fluid concerned in reversible processes, and serve alike for the
demonstration of general theorems and the numerical solution of
particular problems, it is the general if not the universal practice to
use diagrams in which the rectilinear co-ordinates represent volume
and pressure. The object of this article is to call attention to certain
diagrams of different construction, which afford graphical methods co-
extensive in their applications with that in ordinary use, and prefer-
able to it in many cases in respect of distinctness or of convenience.
Quantities and Relations which are to be represented by the
Diagram.
We have to consider the following quantities : —
v, the volume,
p, the pressure,
t, the (absolute) temperature,
e, the energy,
r\, the entropy,
> of a given body in any state,
also W, the work done, 1 by the body in passing from one state
and H, the heat received,* J to another.
* Work spent upon the body is as usual to be considered as a negative quantity of
work done by the body, and heat given out by the body as a negative quantity of heat
received by it.
It is taken for granted that the body has a uniform temperature throughout, and that
the pressure (or expansive force) has a uniform value both for all points in the body and
for all directions. This, it will be observed, will exclude irreversible processes, but will
not entirely exclude solids, although the condition of equal pressure in all directions
renders the case very limited, in which they come within the scope of the discussion.
G. I. A
2 GRAPHICAL METHODS IN THE
These are subject to the relations expressed by the following differ-
ential equations :— dW=«p&>, (a)
de = pdH-dW, (b)
, dH*
dn=— , (c)
where a and /3 are constants depending upon the units by which v, p,
W and H are measured. We may suppose our units so chosen that
a = l and /3=l,t and write our equations in the simpler form,
de = dH-dW, (1)
dW=pdv, (2)
dH=tdtj. (3)
Eliminating dW and dH, we have
de i= F<## — "p dv. (4)
The quantities v, p, t, e and i\ are determined when the state of the
body is given, and it may be permitted to call them functions of the
state of the body, The state of a body, in the sense in which the
term is used in the thermodynamics of fluids, is capable of two inde-
pendent variations, so that between the five quantities v, p, t, 6 and r\
there exist relations expressible by three finite equations, different in
general for different substances, but always such as to be in harmony
with the differential equation (4). This equation evidently signifies
that if e be expressed as function of v and rj, the partial differential
co-efficients of this function taken with respect to v and to r\ will be
equal to — p and to t respectively. {
* Equation (a) may be derived from simple mechanical considerations. Equations (b)
and (c) may be considered as defining the energy and entropy of any state of the body,
or more strictly as defining the differentials de and d-rj. That functions of the state of
the body exist, the differentials of which satisfy these equations, may easily be deduced
from the first and second laws of thermodynamics. The term entropy, it will be
observed, is here used in accordance with the original suggestion of Clausius, and not
in the sense in which it has been employed by Professor Tait and others after his
suggestion. The same quantity has been called by Professor Rankine the Thermo-
dynamic function. See Clausius, Mechanische Wdrmetheorie, Abhnd. ix. § 14 ; or Pogg.
Ann., Bd. cxxv. (1865), p. 390; and Rankine, Phil. Trans., vol. 144, p. 126.
f For example, we may choose as the unit of volume, the cube of the unit of length, —
as the unit of pressure the unit of force acting upon the square of the unit of length, —
as the unit of work the unit of force acting through the unit of length, — and as the unit
of heat the thermal equivalent of the unit of work. The units of length and of force
would still be arbitrary as well as the unit of temperature.
| An equation giving c in terms of TJ and v, or more generally any finite equation
between e, i\ and v for a definite quantity of any fluid, may be considered as the funda-
mental thermodynamic equation of that fluid, as from it by aid of equations (2), (3) and
(4) may be derived all the thermodynamic properties of the fluid (so far as reversible
processes are concerned), viz. : the fundamental equation with equation (4) gives the
three relations existing between v, p, tt e and rj, and these relations being known,
equations (2) and (3) give the work W and heat H for any change of state of the fluid.
THERMODYNAMICS OF FLUIDS. 3
On the other hand W and H are not functions of the state of the
body (or functions of any of the quantities v, p, t, e and rj), but are
determined by the whole series of states through which the body is
supposed to pass.
Fundamental Idea and General Properties of the Diagram.
Now if we associate a particular point in a plane with every separate
state, of which the body is capable, in any continuous manner, so that
states differing infinitely little are associated with points which are
infinitely near to each other,* the points associated with states of
equal volume will form lines, which may be called lines of equal
volume, the different lines being distinguished by the numerical value
of the volume (as lines of volume 10, 20, 30, etc.). In the same way
we may conceive of lines of equal pressure, of equal temperature, of
equal energy, and of equal entropy. These lines we may also call
isometric, isopiestic, isothermal, isodynamic, isentropicj and if neces-
sary use these words as substantives.
Suppose the body to change its state, the points associated with the
states through which the body passes will form a line, which we may
call the path of the body. The conception of a path must include
the idea of direction, to express the order in which the body passes
through the series of states. With every such change of state there
is connected in general a certain amount of work done, W, and of heat
received, H, which we may call the work and the heat of the path. I
The value of these quantities may be calculated from equations (2)
and (3),
dW=pdv,
W=fpdv, (5)
; (6)
* The method usually employed in treatises on thermodynamics, in which the rect-
angular co-ordinates of the point are made proportional to the volume and pressure of
the body, is a single example of such an association.
t These lines are usually known by the name given them by Rankine, adiabatic. If,
however, we follow the suggestion of Clausius and call that quantity entropy, which
Rankine called the thermodynamic function, it seems natural to go one step farther, and
call the lines in which this quantity has a constant value isentropic.
+ For the sake of brevity, it will be convenient to use language which attributes to
the diagram properties which belong to the associated states of the body. Thus it can
give rise to no ambiguity, if we speak of the volume or the temperature of a point in the
diagram, or of the work or heat of a line, instead of the volume or temperature of the
body in the state associated with the point, or the work done or the heat received by
the body in passing through the states associated with the points of the line. In like
manner also we may speak of the body moving along a line in the diagram, instead of
passing through the series of states represented by the line.
4
GRAPHICAL METHODS IN THE
the integration being carried on from the beginning to the end of the
path. If the direction of the path is reversed, W and H change their
signs, remaining the same in absolute value.
If the changes of state of the body form a cycle, i.e., if the final
state is the same as the initial, the path becomes a circuit, and the
work done and heat received are equal, as may be seen from equation
(1), which when integrated for this case becomes 0 = H— W.
The circuit will enclose a certain area, which we may consider as
positive or negative according to the direction of the circuit which
circumscribes it. The direction in which areas must be circumscribed
in order that their value may be positive, is of course arbitrary. In
other words, if x and y are the rectangular co-ordinates, we may
define an area either a.sj'ydx, or &sjxdy.
If an area be divided into any number of parts, the work done in
the circuit bounding the whole area is equal to the sum of the work
done in all the circuits bounding the partial areas. This is evident
from the consideration, that the work done in each of the lines which
separate the partial areas appears twice and with contrary signs in
the sum of the work done in the circuits bounding the partial areas.
Also the heat received in the circuit bounding the whole area is equal
to the sum of the heat received in all the circuits bounding the
partial areas.*
If all the dimensions of a circuit are infinitely small, the ratio of.
the included area to the work or heat of the circuit is independent of
the shape of the circuit and the
direction in which it is described,
and varies only with its position
in the diagram. That this ratio
is independent of the direction in
which the circuit is described, is
evident from the consideration
that a reversal of this direction
simply changes the sign of both
terms of the ratio. To prove that
the ratio is independent of the
shape of the circuit, let us suppose
Fig> L the area ABODE (fig. 1) divided
up by an infinite number of isometrics v^ov V2v2, etc., with equal
differences of volume dv, and an infinite number of isopiestics plpl,
P2p2, etc., with equal differences of pressure dp. Now from the
* The conception of areas as positive or negative renders it unnecessary in propositions
of this kind to state explicitly the direction in which the circuits are to be described.
For the directions of the circuits are determined by the signs of the areas, and the signs
of the partial areas must be the same as that of the area out of which they were formed.
THERMODYNAMICS OF FLUIDS. 5
principle of continuity, as the whole figure is infinitely small, the
ratio of the area of one of the small quadrilaterals into which the
figure is divided to the work done in passing around it is approxi-
mately the same for all the different quadrilaterals. Therefore
the area of the figure composed of all the complete quadrilaterals
which fall within the given circuit has to the work done in circum-
scribing this figure the same ratio, which we will call y. But the
area of this figure is approximately the same as that of the given
circuit, and the work done in describing this figure is approximately
the same as that done in describing the given circuit (eq. 5). There-
fore the area of the given circuit has to the work done or heat received
in that circuit this ratio y, which is independent of the shape of
the circuit.
Now if we imagine the systems of equidifferent isometrics and
isopiestics, which have just been spoken of, extended over the whole
diagram, the work done in circumscribing one of the small quadri-
laterals, so that the increase of pressure directly precedes the increase
of volume, will have in every part of the diagram a constant value,
viz., the product of the differences of volume and pressure (dv x dp),
as may easily be proved by applying equation (2) successively to its
four sides. But the area of one of these quadrilaterals, which we
could consider as constant within the limits of the infinitely small
circuit, may vary for different parts of the diagram, and will indicate
proportionally the value of y, which is equal to the area divided by
dvxdp.
In like manner, if we imagine systems of isentropics and isother-
mals drawn throughout the diagram for equal differences drj and dt,
the heat received in passing around one of the small quadrilaterals,
so that the increase of t shall directly precede that of q, will be the
constant product dr\ X dt, as may be proved by equation (3), and the
value of y, which is equal to the area divided by the heat, will be
indicated proportionally by the areas.*
* The indication of the value of y by systems of equidifferent isometrics and isopies-
tics, or isentropics and isothermals, is explained above, because it seems in accordance
with the spirit of the graphical method, and because it avoids the extraneous consider-
ation of the co-ordinates. If, however, it is desired to have analytical expressions for
the value of y based upon the relations between the co-ordinates of the point and the
state of the body, it is easy to deduce such expressions as the following, in which a;
and y are the rectangular co-ordinates, and it is supposed that the sign of an area is
determined in accordance with the equation A = fydjx : —
l_dv dp dp rfv _ C/T; £^_^& &H
y~ dx dy dx' dy~ dx ' dy dx dy
where x and y are regarded as the independent variables ; — or
_dx dy dy dx •
dv dp dv dp'
6 GRAPHICAL METHODS IN THE
This quantity y, which is the ratio of the area of an infinitely small
circuit to the work done or heat received in that circuit, and which
we may call the scale on which work and heat are represented by
areas, or more briefly, the scale of work and heat, may have a constant
value throughout the diagram or it may have a varying value. The
diagram in ordinary use affords an example of the first case, as the
area of a circuit is everywhere proportional to the work or heat.
There are other diagrams which have the same property, and we may
call all such diagrams of constant scale.
In any case we may consider the scale of work and heat as known
for every point of the diagram, so far as we are able to draw the
isometrics and isopiestics or the isentropics and isothermals. If we
write SW and SH for the work and heat of an infinitesimal circuit,
and SA for the area included, the relations of these quantities are
thus expressed : — *
(7)
We may find the value of W and H for a circuit of finite dimensions
by supposing the included area A divided into areas SA infinitely
small in all directions, for which therefore the above equation will
hold, and taking the sum of the values of 8H or SW for the various
areas 8 A. Writing Wc and H° for the work and heat of the circuit
(7, and 2a for a summation or integration performed within the
limits of this circuit, we have
where v and p are the independent variables ;— or
dx dy du
*y —— _ 9 _ v. _ _ *?_
dr) dt dr}
where rj and t are the independent variables ; — or
1 __ dv drj
y dx dy dy dx
dv drj dv dr)
where v and rj are the independent variables.
These and similar expressions for - may be found by dividing the value of the work
or heat for an infinitely small circuit by the area included. This operation can be most
conveniently performed upon a circuit consisting of four lines, in each of which one of
the independent variables is constant. E.g., the last formula can be most easily found
from an infinitely small circuit formed of two isometrics and two isentropics.
*To avoid confusion, as dW and dH are generally used and are used elsewhere in
this article to denote the work and heat of an infinite short path, a slightly different
notation, 5 W and dH, is here used to denote the work and heat of an infinitely small
circuit. So 8A is used to denote an element of area which is infinitely small in all
directions, as the letter d would only imply that the element was infinitely small in one
direction. So also below, the integration or summation which extends to all the ele-
ments written with 5 is denoted by the character S, as the character /* naturally
refers to elements written with d.
THERMODYNAMICS OF FLUIDS.
(8)
y
We have thus an expression for the value of the work and heat of a
circuit involving an integration extending over an area instead of one
extending over a line, as in equations (5) and (6).
Similar expressions may be found for the work and the heat of a
path which is not a circuit. For this case may be reduced to the
preceding by the consideration that TF=0 for a path on an iso-
inetric or on the line of no pressure (eq. 2), and H=0 for a path on
an isentropic or on the line of absolute cold. Hence the work of any
path $ is equal to that of the circuit formed of S, the isometric of
the final state, the line of no pressure and the isometric of the initial
state, which circuit may be represented by the notation [S, v", p°, v'].
And the heat of the same path is the same as that of the circuit [8, if,
tQ, if]. Therefore using Ws and H8 to denote the work and heat of
any path S, we have
' • ' (9)
where as before the limits of the integration are denoted by the
expression occupying the place of an index to the sign 2.* These
equations evidently include equation (8) as a particular case.
It is easy to form a material conception of these relations. If we
imagine, for example, mass inherent in the plane of the diagram with
a varying (superficial) density represented by -, then 2 - 8 A will
_ y y
*A word should be said in regard to the sense in which the above propositions
should be understood. If beyond the limits, within which the relations of v, />, t, e
and T/ are known and which we may call the limits of the known field, we continue the
isometrics, isopiestics, &c., in any way we please, only subject to the condition that the
relations of ?;, p, t, e and 17 shall be consistent with the equation de = tdrj- pdv, then in
calculating the values of quantities W and H determined by the equations d W=pdv
and dH=td-rj for paths or circuits in any part of the diagram thus extended, we may
use any of the propositions or processes given above, as these three equations have
formed the only basis of the reasoning. We will thus obtain values of W and H, which
will be identical with those which would be obtained by the immediate application of
the equations dW=pdv and dH=td-rj to the path in question, and which in the case of
any path which is entirely contained in the known field will be the true values of the
work and heat for the change of state of the body which the path represents. We
may thus use lines outside of the known field without attributing to them any physical
signification whatever, without considering the points in the lines as representing any
states of the body. If however, to fix our ideas, we choose to conceive of this part of
the diagram as having the same physical interpretation as the known field, and to
enunciate our propositions in language based upon such a conception, the unreality or
even the impossibility of the states represented by the lines outside of the known field
cannot lead to any incorrect results in regard to paths in the known field.
8 GRAPHICAL METHODS IN THE
evidently denote the mass of the part of the plane included within
the limits of integration, this mass being taken positively or nega-
tively according to the direction of the circuit.
Thus far we have made no supposition in regard to the nature of
the law, by which we associate the points of a plane with the states
of the body, except a certain condition of continuity. Whatever law
we may adopt, we obtain a method of representation of the thermo-
dynamic properties of the body, in which the relations existing
between the functions of the state of the body are indicated by a
net- work of lines, while the work done and the heat received by the
body when it changes its state are represented by integrals extend-
ing over the elements of a line, and also by an integral extending
over the elements of certain areas in the diagram, or, if we choose to
introduce such a consideration, by the mass belonging to these areas.
The different diagrams which we obtain by different laws of asso-
ciation are all such as may be obtained from one another by a process
of deformation, and this consideration is sufficient to demonstrate
their properties from the well-known properties of the diagram in
which the volume and pressure are represented by rectangular co-
ordinates. For the relations indicated by the net- work of isometrics,
isopiestics etc., are evidently not altered by deformation of the sur-
face upon which they are drawn, and if we conceive of mass as belong-
ing to the surface, the mass included within given lines will also not
be affected by the process of deformation. If, then, the surface upon
which the ordinary diagram is drawn has the uniform superficial den-
sity 1, so that the work and heat of a circuit, which are represented
in this diagram by the included area, shall also be represented by
the mass included, this latter relation will hold for any diagram
formed from this by deformation of the surface on which it is drawn.
The choice of the method of representation is of course to be deter-
mined by considerations of simplicity and convenience, especially in
regard to the drawing of the lines of equal volume, pressure, tempera-
ture, energy and entropy, and the estimation of work and heat. There
is an obvious advantage in the use of diagrams of constant scale, in
which the work and heat are represented simply by areas. Such dia-
grams may of course be produced by an infinity of different methods,
as there is no limit to the ways of deforming a plane figure without
altering the magnitude of its elements. Among these methods, two
are especially important, — the ordinary method in which the volume
and pressure are represented by rectilinear co-ordinates, and that in
which the entropy and temperature are so represented. A diagram
formed by the former method may be called, for the sake of distinc-
tion, a volume-pressure diagram, — one formed by the latter, an entropy -
temperature diagram. That the latter as well as the former satisfies
THERMODYNAMICS OF FLUIDS. 9
the condition that y = 1 throughout the whole diagram, may be seen
by reference to page 5.
The Entropy-temperature Diagram compared with that in
ordinary use.
Considerations independent of the nature of the body in question.
As the general equations (1), (2), (3) are not altered by interchang-
ing v, —p and — W with q, t and H respectively, it is evident that,
so far as these equations are concerned, there is nothing to choose
between a volume-pressure and an entropy-temperature diagram. In
the former, the work is represented by an area bounded by the path
which represents the change of state of the body, two ordinates and
the axis of abscissas. The same is true of the heat received in the
latter diagram. Again, in the former diagram, the heat received is
represented by an area bounded by the path and certain lines, the
character of which depends upon the nature of the body under consid-
eration. Except in the case of an ideal body, the properties of which
are determined by assumption, these lines are more or less unknown
in a part of their course, and in any case the area will generally
extend to an infinite distance. Very much the same inconveniences
attach themselves to the areas representing work in the entropy-
temperature diagram.* There is, however, a consideration of a
*In neither diagram do these circumstances create any serious difficulty in the esti-
mation of areas representing work or heat. It is always possible to divide these areas
into two parts, of which one is of finite dimensions, and the other can be calculated in
the simplest manner. Thus in the entropy-tempera-
ture diagram the work done in a path AB (fig. 2) is
represented by the area included by the path AB, the
isometric BC, the line of no pressure and the isometric
DA. The line of no pressure and the adjacent parts
of the isometrics in the case of an actual gas or vapor
are more or less undetermined in the present state
of our knowledge, and are likely to remain so ; for
an ideal gas the line of no pressure coincides with
the axis of abscissas, and is an asymptote to the
isometrics. But, be this as it may, it is not necessary Fig. 2.
to examine the form of the remoter parts of the
diagram. If we draw an isopiestic MN, cutting AD and BC, the area MNCD, which
represents the work done in MN, will be equal to p(tf - 1/), where p denotes the pressure
in MN, and v" and v' denote the volumes at B and A respectively (eq. 5). Hence the
work done in AB will be represented by ABNM+p(t/'- 1/). In the volume-pressure
diagram, the areas representing heat may be divided by an isothermal, and treated in
a manner entirely analogous.
Or we may make use of the principle that, for a path which begins and ends on the
same isodynamic, the work and heat are equal, as appears by integration of equation
(1). Hence, in the entropy-temperature diagram, to find the work of any path, we may
extend it by an isometric (which will not alter its work), so that it shall begin and end
10
GKAPHICAL METHODS IN THE
general character, which shows an important advantage on the side of
the entropy-temperature diagram. In thermodynamic problems, heat
received at one temperature is by no means the equivalent of the
same amount of heat received at another temperature. For example,
a supply of a million calories at 150C is a very different thing from a
supply of a million calories at 50C. But no such distinction exists in
regard to work. This is a result of the general law, that heat can
only pass from a hotter to a colder body, while work can be transferred
by mechanical means from one fluid to any other, whatever may be
the pressures. Hence, in thermodynamic problems, it is generally
necessary to distinguish between the quantities of heat received or
given out by the body at different temperatures, while as far as work
is concerned, it is generally sufficient to ascertain the total amount
performed. If, then, several heat-areas and one work-area enter into
the problem, it is evidently more important that the former should be
simple in form, than that the latter should be so. Moreover, in the
very common case of a circuit, the work-area is bounded entirely by
the path, and the form of the isometrics and the line of no pressure
are of no especial consequence.
It is worthy of notice that the simplest form of a perfect thermo-
dynamic engine, so often described in treatises on thermodynamics, is
represented in the entropy-temperature
diagram by a figure of extreme sim-
plicity, viz: a rectangle of which the
sides are parallel to the co-ordinate
axes. Thus in figure 3, the circuit
ABCD may represent the series of
states through which the fluid is made
to pass in such an engine, the included
77 area representing the work done, while
the area ABFE represents the heat
received from the heater at the highest temperature AE, and the
area CDEF represents the heat transmitted to the cooler at the lowest
temperature DE.
There is another form of the perfect thermodynamic engine, viz :
one with a perfect regenerator as defined by Rankine, Phil. Trans.
vol. 144, p. 140, the representation of which becomes peculiarly
simple in the entropy-temperature diagram. The circuit consists of
two equal straight lines AB and CD (fig. 4) parallel to the axis of
abscissas, and two precisely similar curves of any form BC and AD.
on the same isodynamic, and then take the heat (instead of the work) of the path thus
extended. This method was suggested by that employed by Cazin, Theorie eUmvn,-
taire den machines a air chaud, p. 11, and Zeuner, Mechanische Warmetheorie, p. 80,
in the reverse case, viz : to find the heat of a path in the volume-pressure diagram.
0
E
Fig. 3.
THERMODYNAMICS OF FLUIDS.
11
B
The included area ABCD represents the work done, and the areas
ABba and CDdc represent respectively the heat received from the
heater and that transmitted to the
cooler. The heat imparted by the fluid
to the regenerator in passing from B
to C, and afterward restored to the
fluid in its passage from D to A, is
represented by the areas BCcb and
DAad.
It is often a matter of the first
importance in the study of any thermo-
dynamic engine, to compare it with a
o
Fig. 4.
perfect engine. Such a comparison will obviously be much facilitated
by the use of a method in which the perfect engine is represented
by such simple forms.
The method in which the co-ordinates represent volume and pressure
has a certain advantage in the simple and elementary character of the
notions upon which it is based, and its analogy with Watt's indicator
has doubtless contributed to render it popular. On the other hand,
a method involving the notion of entropy, the very existence of which
depends upon the second law of thermodynamics, will doubtless seem
to many far-fetched, and may repel beginners as obscure and difficult
of comprehension. This inconvenience is perhaps more than counter-
balanced by the advantages of a method which makes the second law
of thermodynamics so prominent, and gives it so clear and elementary
an expression. The fact, that the different states of a fluid can be
represented by the positions of a point in a plane, so that the ordi-
iiates shall represent the temperatures, and the heat received or given
out by the fluid shall be represented by the area bounded by the line
representing the states through which the body passes, the ordinates
drawn through the extreme points of this line, and the axis of
abscissas, — this fact, clumsy as its expression in words may be, is one
which presents a clear image to the eye, and which the mind can
readily grasp and retain. It is, however, nothing more nor less than
a geometrical expression of the second law of thermodynamics in its
application to fluids, in a form exceedingly convenient for use, and
from which the analytical expression of the same law can, if desired,
be at once obtained. If, then, it is more important for purposes of
instruction and the like to familiarize the learner with the second
law, than to defer its statement as long as possible, the use of the
entropy-temperature diagram may serve a useful purpose in the
popularizing of this science.
The foregoing considerations are in the main of a general character,
and independent of the nature of the substance to which the graphical
12
method is applied. On this, however, depend the forms of the
isometrics, isopiestics and isodynamics in the entropy-temperature
diagram, and of the isentropics, isothermals and isodynamics in the
volume-pressure diagram. As the convenience of a method depends
largely upon the ease with which these lines can be drawn, and upon
the peculiarities of the fluid which has its properties represented in
the diagram, it is desirable to compare the methods under considera-
tion in some of their most important applications. We will commence
with the case of a perfect gas.
Case of a perfect gas.
A perfect or ideal gas may be defined as such a gas, that for any
constant quantity of it the product of the volume and the pressure
varies as the temperature, and the energy varies as the temperature, i.e.,,
*
pv = att (A)
e = ct. (B)
C "*"
The significance of the constant a is sufficiently indicated by equation
(A). The significance of c may be rendered more evident by differen-
tiating equation (B) and comparing the result
de — cdt
with the general equations (1) and (2), viz :
If dv = 0, dW=0, and dH=cdt, i.e.,
(dH\
\dt)-°'~*
i.e., c is the quantity of heat necessary to raise the temperature of
the body one degree under the condition of constant volume. It will
be observed, that when different quantities of the same gas are con-
sidered, a and c both vary as the quantity, and c-i-a is constant; also,
that the value of c+a for different gases varies as their specific heat
determined for equal volumes and for constant volume.
With the aid of equations (A) and (B) we may eliminate p and t
from the general equation (4), viz :
*In this article, all equations which are designated by arabic numerals subsist for
any body whatever (subject to the condition of uniform pressure and temperature), and
those which are designated by small capitals subsist for any quantity of a perfect gas
as defined above (subject of course to the same conditions).
t A subscript letter after a differential co-efficient is used in this article to indicate-
the quantity which is made constant in the differentiation.
THERMODYNAMICS OF FLUIDS. 13
,.,.,, de I j a dv
which is then reduced to -=~dn — — ,
e c c v
and by integration to loge=- — logv.* (D)
c c
The constant of integration becomes 0, if we call the entropy 0 for
the state of which the volume and energy are both unity.
Any other equations which subsist between v, p, t, e and r\ may be
derived from the three independent equations (A), (B) and (D). If we
eliminate e from (B) and (D), we have
7/ = alog/y + clog^H-clogc. (E)
Eliminating v from (A) and (E), we have
tj = (a+c)\ogt — alogp+clogc+aloga. (F)
Eliminating t from (A) and (E), we have
/»
ij = (a+c)logv+clogp+c\og-. (a)
ot
If v is constant, equation (E) becomes
T] = c log t + Const.,
i.e., the isometrics in the entropy-temperature diagram are logarithmic
curves identical with one another in form, — a change in the value of
v having only the effect of moving the curve parallel to the axis of tj.
If p is constant, equation (F) becomes
T] = (a + c) log t + Const.,
so that the isopiestics in this diagram have similar properties. This
identity in form diminishes greatly the labour of drawing any con-
siderable number of these curves. For if a card or thin board be cut
in the form of one of them, it may be used as a pattern or ruler to
draw all of the same system.
The isodynamics are straight in this diagram (eq. B).
To find the form of the isothermals and isentropics in the volume-
pressure diagram, we may make t and r\ constant in equations (A)
and (G) respectively, which will then reduce to the well-known equa-
tions of these curves : —
pv — Const.,
and cva+c — Const.
*If we use the letter « to denote the base of the Naperian system of logarithms,
equation (D) may also be written in the form
This may be regarded as the fundamental thermodynamic equation of an ideal gas. See
the last note on page 2. It will be observed, that there would be no real loss of
generality if we should choose, as the body to which the letters refer, such a quantity
of the gas that one of the constants a and c should be equal to unity.
14 GRAPHICAL METHODS IN THE
The equation of the isodynamics is of course the same as that of the
isothermals. None of these systems of lines have that property of
identity of form, which makes the systems of isometrics and isopiestics
so easy to draw in the entropy-temperature diagram.
Case of condensable vapors.
The case of bodies which pass from the liquid to the gaseous condi-
tion is next to be considered. It is usual to assume of such a body,
that when sufficiently superheated it approaches the condition of a
perfect gas. If, then, in the entropy-temperature diagram of such a
body we draw systems of isometrics, isopiestics and isodynamics, as if
for a perfect gas, for proper values of the constants a and c, these will
be asymptotes to the true isometrics, etc., of the vapor, and in many
cases will not vary from them greatly in the part of the diagram which
represents vapor unmixed with liquid, except in the vicinity of the
line of saturation. In the volume-pressure diagram of the same body,
the isothermals, isentropics and isodynamics, drawn for a perfect gas
for the same values of a and c, will have the same relations to the true
isothermals, etc.
In that part of any diagram which represents a mixture of vapor
and liquid, the isopiestics and isothermals will be identical, as the
pressure is determined by the temperature alone. In both the
diagrams which we are now comparing, they will be straight and
parallel to the axis of abscissas. The form of the isometrics and
isodynamics in the entropy-temperature diagram, or that of the
isentropics and isodynamics in the volume-pressure diagram, will
depend upon the nature of the fluid, and probably cannot be ex-
pressed by any simple equations. The following property, however,
renders it easy to construct equidifferent systems of these lines, viz :
any such system will divide any isothermal (isopiestic) into equal
segments.
It remains to consider that part of the diagram which represents
the body when entirely in the condition of liquid. The fundamental
characteristic of this condition of matter is that the volume is very
nearly constant, so that variations of volume are generally entirely in-
appreciable when represented graphically on the same scale on which
the volume of the body in the state of vapor is represented, and both
the variations of volume and the connected variations of the connected
quantities may be, and generally are, neglected by the side of the
variations of the same quantities which occur when the body passes
to the state of vapor.
Let us make, then, the usual assumption that v is constant, and see
how the general equations (1), (2), (3) and (4) are thereby affected.
THERMODYNAMICS OF FLUIDS. 15
We have first,
dv = 0,
then dW=Q,
and de =t drj.
If we add dH = t dtj,
these four equations will evidently be equivalent to the three inde-
pendent equations (1), (2) and (3), combined with the assumption
which we have just made. For a liquid, then, e, instead of being a
function of two quantities v and t], is a function of rj alone, — t is also
a function of jj alone, being equal to the differential co-efficient of the
function e ; that is, the value of one of the three quantities t, e and jy,
is sufficient to determine the other two. The value of v, moreover, is
fixed without reference to the values of t, e and r\ (so long as these do
not pass the limits of values possible for liquidity); while p does not
enter into the equations, i.e., p may have any value (within certain
limits) without affecting the values of t, e, rj or v. If the body change
its state, continuing always liquid, the value of W for such a change
is 0, and that of H is determined by the values of any one of the
three quantities t, e and tj. It is, therefore, the relations between t, e,
ij and H, for which a graphical expression is to be sought ; a method,
therefore, in which the co-ordinates of the diagram are made equal
to the volume and pressure, is totally inapplicable to this particu-
lar case ; v and p are indeed the only two of the five functions of the
state of the body, v, p, t, e and rj, which have no relations either to
each other, or to the other three, or to the quantities W and H, to be
expressed.* The values of v and p do not really determine the state
of an incompressible fluid, — the values of t, € and ;/ are still left
undetermined, so that through every point in the volume-pressure
diagram which represents the liquid there must pass (in general) an
infinite number of isothermals, isodynamics and isentropics. The
character of this part of the diagram is as follows : — the states of
liquidity are represented by the points of a line parallel to the axis of
pressures, and the isothermals, isodynamics and isentropics, which
cross the field of partial vaporization and meet this line, turn upward
and follow its course.!
In the entropy-temperature diagram the relations of t, e and jj are
* That is, v and p have no such relations to the other quantities, as are expressible
by equations ; p, however, cannot be less than a certain function of t.
t All these difficulties are of course removed when the differences of volume of the
liquid at different temperatures are rendered appreciable on the volume-pressure
diagram. This can be done in various ways, — among others, by choosing as the body
to which t?, etc., refer, a sufficiently large quantity of the fluid. But, however we do it,
we must evidently give up the possibility of representing the body in the state of vapor
in the same diagram without making its dimensions enormous.
16
GRAPHICAL METHODS IN THE
distinctly visible. The line of liquidity is a curve AB (fig. 5) deter-
mined by the relation between t and ^. This curve is also an iso-
metric. Every point of it has a definite
volume, temperature, entropy and
energy. The latter is indicated by the
isodynamics E1E1, E2E2, etc., which
cross the region of partial vaporization
and terminate in the line of liquidity.
(They do not in this diagram turn and
follow the line.) If the body pass
from one state to another, remaining
liquid, as from M to N in the figure,
the heat received is represented as
_^ usual by the area MNnm. That the
r> work done is nothing, is indicated
by the fact that the line AB is an
isometric. Only the isopiestics in this diagram are superposed in
the line of fluidity, turning downward where they meet this line and
following its course, so that for any point in this line the pressure is
undetermined. This is, however, no inconvenience in the diagram, as
it simply expresses the fact of the case, that when all the quantities
v, t, e and ij are fixed, the pressure is still undetermined.
0
m n
Fig. 5.
Diagrams in which the Isometrics, Isopiestics, Isothermals, Iso-
dynamics and Isentropics of a Perfect Gas are all Straight
Lines.
There are many cases in which it is of more importance that it
should be easy to draw the lines of equal volume, pressure, tempera-
ture, energy and entropy, than that work and heat should be repre-
sented in the simplest manner. In such cases it may be expedient to
give up the condition that the scale (y) of work and heat shall be
constant, when by that means it is possible to gain greater simplicity
in the form of the lines just mentioned.
In the case of a perfect gas, the three relations between the quanti-
ties v, p, t, e and rj are given on pages 12, 13, equations (A), (B) and (D).
These equations may be easily transformed into the three
v — log t = log a, (H)
€ — log t = log C, (l)
j] — c log e — a log v = 0 ; (j)
so that the three relations between the quantities logv, logp, logt,
log e and r\ are expressed by linear equations, and it will be possible
to make the five systems of lines all rectilinear in the same diagram,
THERMODYNAMICS OF FLUIDS.
17
the distances of the isometrics being proportional to the differences
of the logarithms of the volumes, the distances of the isopiestics being
proportional to the differences of the logarithms of the pressures, and
so with the isothermals and the isodynamics, — the distances of the
isentropics, however, being proportional to the differences of entropy
simply.
The scale of work and heat in such a diagram will vary inversely
as the temperature. For if we imagine systems of isentropics and
isothermals drawn throughout the diagram for equal small differences
of entropy and temperature, the isentropics will be equidistant, but
the distances of the isothermals will vary inversely as the temperature,
and the small quadrilaterals into which the diagram is divided will
vary in the same ratio: /. y «* l+t. (See p. 5.)
So far, however, the form of the diagram has not been completely
defined. This may be done in various ways : e.g., if x and y be the
rectangular co-ordinates, we may make
or
' etc.
Or we may set the condition that the logarithms of volume, of pressure
and of temperature, shall be represented
in the diagram on the same scale. (The
logarithms of energy are necessarily re-
presented on the same scale as those of
temperature.) This will require that the
isometrics, isopiestics and isothermals cut
one another at angles of 60°.
The general character of all these dia-
grams, which may be derived from one
another by projection by parallel lines, may
be illustrated by the case in which x = log v ,
and y = \ogp.
Through any point A (fig. 6) of such a
diagram let there be drawn the isometric
vv', the isopiestic pp', the isothermal tt' and the isentropic i\r{. The
lines pp' and vv' are of course parallel to the axes. Also by equation (H)
P'
Fig. 6.
\dlog v
and by (a)
J
c + a
TJ vw *^£> "' 1J
Therefore, if we draw another isometric, cutting TJJJ', tt', and pp' in
B, C and D,
CD_c
"' CD~c BC~~a'
G.I. B
18 GRAPHICAL METHODS IN THE
Hence, in the diagrams of different gases, CD-:-BC will be propor-
tional to the specific heat determined for equal volumes and for
constant volume.
As the specific heat, thus determined, has probably the same value
for most simple gases, the isentropics will have the same inclination
in diagrams of this kind for most simple gases. This inclination may
easily be found by a method which is independent of any units of
measurement, for
BD:CD::
\d log tv, ' \d log v/t ' \dv/^ ' \dv/t
i.e., BD-r-CD is equal to the quotient of the co-efficient of elasticity
under the condition of no transmission of heat, divided by the co-
efficient of elasticity at constant temperature. This quotient for a
simple gas is generally given as 1*408 or 1*421. As
BD is very nearly equal to CA (for simple gases), which relation it
may be convenient to use in the construction of the diagram.
In regard to compound gases the rule seems to be, that the specific
heat (determined for equal volumes and for constant volume) is to the
specific heat of a simple gas inversely as the volume of the compound
is to the volume of its constituents (in the condition of gas) ; that is,
the value of BC-j-CD for a compound gas is to the value of BC-J-CD
for a simple gas, as the volume of the compound is to the volume of
its constituents. Therefore, if we compare the diagrams (formed by
this method) for a simple and a compound gas, the distance DA and
therefore CD being the same in each, BC in the diagram of the com-
pound gas will be to BC in the diagram of the simple gas as the
volume of the compound is to the volume of its constituents.
Although the inclination of the isentropics is independent of the
quantity of gas under consideration, the rate of increase of r\ will vary
with this quantity. In regard to the rate of increase of t, it is evident
that if the whole diagram be divided into squares by isopiestics and
isometrics drawn at equal distances, and isothermals be drawn as
diagonals to these squares, the volumes of the isometrics, the pressures
of the isopiestics and the temperatures of the isothermals will each
form a geometrical series, and in all these series the ratio of two
contiguous terms will be the same.
The properties of the diagrams obtained by the other methods men-
tioned on page 17 do not differ essentially from those just described.
For example, in any such diagram, if through any point we draw an
isentropic, an isothermal and an isopiestic, which cut any isometric
not passing through the same point, the ratio of the segments of the
isometric will have the value which has been found for BC : CD.
In treating the case of vapors also, it may be convenient to use
THERMODYNAMICS OF FLUIDS. 19
diagrams in which x = logv and y = logp, or in which x — r\ and
2/ = log£; but the diagrams formed by these methods will evidently
be radically different from one another. It is to be observed that
each of these methods is what may be called a method of definite scale
for work and heat ; that is, the value of y in any part of the diagram
is independent of the properties of the fluid considered. In the first
method y = -^- , in the second y = — . In this respect these methods
.
have an advantage over many others. For example, if we should
make x = log v, y = r\y the value of y in any part of the diagram would
depend upon the properties of the fluid, and would probably not vary
in any case, except that of a perfect gas, according to any simple law.
The conveniences of the entropy-temperature method will be found
to belong in nearly the same degree to the method in which the
co-ordinates are equal to the entropy and the logarithm of the tem-
perature. No serious difficulty attaches to the estimation of heat and
work in a diagram formed on the latter method on account of the
variation of the scale on which they are represented, as this variation
follows so simple a law. It may often be of use to remember that
such a diagram may be reduced to an entropy-temperature diagram
by a vertical compression or extension, such
that the distances of the isothermals shall be
made proportional to their differences of tem-
perature. Thus if we wish to estimate the work
or heat of the circuit ABCD (fig. 7), we may
draw a number of equidistant ordinates (isen- A
tropics) as if to estimate the included area, and
for each of the ordinates take the differences
of temperature of the points where it cuts the
circuit; these differences of temperature will
be equal to the lengths of the segments made by the corresponding
circuit in the entropy-temperature diagram upon a corresponding
system of equidistant ordinates, and may be used to calculate the
area of the circuit in the entropy-temperature diagram, i.e., to find
the work or heat required. We may find the work of any path by
applying the same process to the circuit formed by the path, the iso-
metric of the final state, the line of no pressure (or any isopiestic ; see
note on page 9), and the isometric of the initial state. And we may
find the heat of any path by applying the same process to a circuit
formed by the path, the ordinates of the extreme points and the line
of absolute cold. That this line is at an infinite distance occasions no
difficulty. The lengths of the ordinates in the entropy-temperature
diagram which we desire are given by the temperature of points in
the path determined (in either diagram) by equidistant ordinates.
20 GRAPHICAL METHODS IN THE
The properties of the part of the entropy-temperature diagram
representing a mixture of vapor and liquid, which are given on
page 14, will evidently not be altered if the ordinates are made
proportional to the logarithms of the temperatures instead of the
temperatures simply.
The representation of specific heat in the diagram under discussion
is peculiarly simple. The specific heat of any substance at constant
volume or under constant pressure may be defined as the value of
(dH\ fdH\ . ( drj \
\dt)vGC \dt)p ' * e*' \d log t)v °
for a certain quantity of the substance. Therefore, if we draw a dia-
gram, in which x = r\ and y — log t, for that quantity of the substance
which is used for the determination of the specific heat, the tangents
of the angles made by the isometrics and the isopiestics with the
ordinates in the diagram will be equal to the specific heat of the
substance determined for constant volume and for constant pressure
respectively. Sometimes, instead of the condition of constant volume
or constant pressure, some other condition is used in the determination
of specific heat. In all cases, the condition will be represented by a
line in the diagram, and the tangent of the angle made by this line
with an ordinate will be equal to the specific heat as thus defined. If
the diagram be drawn for any other quantity of the substance, the
specific heat for constant volume or constant pressure, or for any other
condition, will be equal to the tangent of the proper angle in the
diagram, multiplied by the ratio of the quantity of the substance for
which the specific heat is determined to the quantity for which the
diagram is drawn.*
The Volume-entropy Diagram.
The method of representation, in which the co-ordinates of the point
in the diagram are made equal to the volume and entropy of the
body, presents certain characteristics which entitle it to a somewhat
detailed consideration, and for some purposes give it substantial
advantages over any other method. We might anticipate some of
these advantages from the simple and symmetrical form of the general
equations of thermodynamics, when volume and entropy are chosen
as independent variables, viz : — t
*From this general property of the diagram, its character in the case of a perfect
gas might be immediately deduced.
t See page 2, equations (2), (3) and (4).
In general, in this article, where differential coefficients are used, the quantity which
is constant in the differentiation is indicated by a subscript letter. In this discussion
of the volume-entropy diagram, however, v and 77 are uniformly regarded as the inde-
pendent variables, and the subscript letter is omitted.
THERMODYNAMICS OF FLUIDS. 21
«-a?
dW=pdv,
dH=tdrj.
Eliminating p and t we have also
-gjCto, (13)
dn. (14)
The geometrical relations corresponding to these equations are in
the volume-entropy diagram extremely simple. To fix our ideas, let
the axes of volume and entropy be horizontal and vertical respec-
tively, volume increasing toward the right and entropy upward.
Then the pressure taken negatively will equal the ratio of the differ-
ence of energy to the difference of volume of two adjacent points in
the same horizontal line, and the temperature will equal the ratio of
the difference of energy to the difference of entropy of two adjacent
points in the same vertical line. Or, if a series of isodynamics be
drawn for equal infinitesimal differences of energy, any series of hori-
zontal lines will be divided into segments inversely proportional to
the pressure, and any series of vertical lines into segments inversely
proportional to the temperature. We see by equations (13) and (14),
that for a motion parallel to the axis of volume, the heat received is
0, and the work done is equal to the decrease of the energy, while for
a motion parallel to the axis of entropy, the work done is 0, and the
heat received is equal to the increase of the energy. These two
propositions are true either for elementary paths or for those of finite
length. In general, the work for any element of a path is equal to
the product of the pressure in that part of the diagram into the hori-
zontal projection of the element of the path, and the heat received is
equal to the product of the temperature into the vertical projection
of the element of the path.
If we wish to estimate the value of the integrals fpdv and ftdr\,
which represent the work and heat of any path, by means of measure-
ments upon the diagram, or if we wish to appreciate readily by the
eye the approximate value of these expressions, or if we merely wish
to illustrate their meaning by means of the diagram ; for any of these
purposes the diagram which we are now considering will have the
advantage that it represents the differentials dv and drj more simply
and clearly than any other.
22 GRAPHICAL METHODS IN THE
But we may also estimate the work and heat of any path by means
of an integration extending over the elements of an area, viz : by the
formulae of page 7,
r
In regard to the limits of integration in these formulae, we see that for
the work of any path which is not a circuit, the bounding line is com-
posed of the path, the line of no pressure and two vertical lines, and
for the heat of the path, the bounding line is composed of the path,
the line of absolute cold and two horizontal lines.
As the sign of y, as well as that of 8 A, will be indeterminate until
we decide in which direction an area must be circumscribed in order
to be considered positive, we will call an area positive which is cir-
cumscribed in the direction in which the hands of a watch move.
This choice, with the positions of the axes of volume and entropy
which we have supposed, will make the value of y in most cases posi-
tive, as we shall see hereafter.
The value of y, in a diagram drawn according to this method, will
depend upon the properties of the body for which the diagram is
drawn. M this respect, this method
differs from all the others which have
been discussed in detail in this article.
It is easy to find an expression for y
depending simply upon the variations of
N • _ N« the energy, by comparing the area and
_ I the work or heat of an infinitely small
N* N» circuit in the form of a rectangle having
its sides parallel to the two axes.
Let N1N2N3N4 (fig. 8) be such a circuit,
and let it be described in the order of
v the numerals, so that the area is positive.
Also let ev e2> e3, e4 represent the energy
at the four corners. The work done in the four sides in order com-
mencing at Np will be e1 — e2, 0, e3 — e4, 0. The total work, therefore,
for the rectangular circuit is
Now as the rectangle is infinitely small, if we call its sides dv and dq,
the above expression will be equivalent to
dze
— -j — 5- dv dn.
dvdrj
THERMODYNAMICS OF FLUIDS. 23
Dividing by the area dv dq, and writing yv> , for the scale of work and
heat in a diagram of this kind, we have
1 dze _dp _ _dt
yV}1l dvdrj dri dv
The two last expressions for the value of 1-r-y^,, indicate that the
value of yVj,, in different parts of the diagram will be indicated pro-
portionally by the segments into which vertical lines are divided by a
system of equidifferent isopiestics, and also by the segments into
which horizontal lines are divided by a system of equidifferent iso-
therrnals. These results might also be derived directly from the
propositions on page 5.
As, in almost all cases, the pressure of a body is increased when it
receives heat without change of volume, -f- is in general positive, and
the same will be true of yv>n under the assumptions which we have
made in regard to the directions of the axes (page 21) and the defini-
tion of a positive area (page 22).
In the estimation of work and heat it may often be of use to
consider the deformation necessary to reduce the diagram to one of
constant scale for work and heat. Now if the diagram be so deformed
that each point remains in the same vertical line, but moves in this
line so that all isopiestics become straight and horizontal lines at
distances proportional to their differences of pressure, it will evidently
become a volume-pressure diagram. Again, if the diagram be so
deformed that each point remains in the same horizontal line, but
moves in it so that isothermals become straight and vertical lines at
distances proportional to their differences of temperature, it will
become an entropy-temperature diagram. These considerations will
enable us to compute numerically the work or heat of any path
which is given in a volume-entropy diagram, when the pressure and
temperature are known for all points of the path, in a manner
analogous to that explained on page 19.
The ratio of any element of area in the volume-pressure or the
entropy- temperature diagram, or in any other in which the scale of
work and heat is unity, to the corresponding element in the volume-
entropy diagram is represented by -or — -T- -,-. The cases in
y«;,ij dvat]
which this ratio is 0, or changes its sign, demand especial attention,
as in such cases the diagrams of constant scale fail to give a satis-
factory representation of the properties of the body, while no difficulty
or inconvenience arises in the use of the volume-entropy diagram.
d c d1^)
As —-, , = j> it8 value is evidently zero in that part of the
diagram which represents the body when in part solid, in part liquid,
24 GRAPHICAL METHODS IN THE
and in part vapor. The properties of such a mixture are very simply
and clearly exhibited in the volume-entropy diagram.
Let the temperature and the pressure of the mixture, which are
independent of the proportions of vapor, solid and liquid, be denoted
by if and p'. Also let V, L and S (fig. 9)
be points of the diagram which indicate
v the volume and entropy of the body in
three perfectly defined states, viz : that of
a vapor of temperature if and pressure p\
that of a liquid of the same temperature
and pressure, and that of a solid of the
same temperature and pressure. And let
vV) i\v, VL, rjL, vs, ris denote the volume and
Fi 9 entropy of these states. The position of
the point which represents the body, when
part is vapor, part liquid, and part solid, these parts being as /*, i/,
and 1 — fji — i/, is determined by the equations
V = fJLV v + WL + (1 - JUL - V)V a,
where v and rj are the volume and entropy of the mixture. The
truth of the first equation is evident. The second may be written
f-Hf
or multiplying by if,
The first member of this equation denotes the heat necessary to 'bring
the body from the state S to the state of the mixture in question
under the constant temperature if, while the terms of the second
member denote separately the heat necessary to vaporize the part ju,
and to liquefy the part v of the body.
The values of v and r\ are such as would give the center of gravity
of masses //, v and 1 — /z — v placed at the points V, L and S.* Hence
the part of the diagram which represents a mixture of vapor, liquid
and solid, is the triangle VLS. The pressure and temperature are
constant for this triangle, i.e., an isopiestic and also an isothermal
here expand to cover a space. The isodynamics are straight and equi-
distant for equal differences of energy. For -7- = —p' and -^~ = t',
both of which are constant throughout the triangle.
* These points will not be in the same straight line unless
t' (nv - rjs) : t'tiL - ifor) : : i>r - vs : VL - vs,
a condition very unlikely to be fulfilled by any substance. The first and second terms
of this proportion denote the heat of vaporization (from the solid state) and that of
liquefaction.
THERMODYNAMICS OF FLUIDS.
This case can be but very imperfectly represented in the volume-
pressure, or in the entropy-temperature diagram. For all points in
the same vertical line in the triangle VLS will, in the volume-pressure
diagram, be represented by a single point, as having the same volume
and pressure. And all the points in the same horizontal line will be
represented in the entropy-temperature diagram by a single point, as
having the same entropy and temperature. In either diagram, the
whole triangle reduces to a straight line. It must reduce to a line
in any diagram whatever of constant scale, as its area must become
0 in such a diagram. This must be regarded as a defect in these
diagrams, as essentially different states are represented by the same
point. In consequence, any circuit within the triangle VLS will be
represented in any diagram of constant scale by two paths of opposite
directions superposed, the appearance being as if a body should change
its state and then return to its original state by inverse processes, so
as to repass through the same series of states. It is true that the
circuit in question is like this combination of processes in one important
particular, viz : that W= H=0, i.e., there is no transformation of heat
into work. But this very fact, that a circuit without transformation
of heat into work is possible, is worthy of distinct representation.
A body may have such properties that in one part of the volume-
entropy diagram
dp
i.e., -f
dq
is
positive and in another negative.
These parts of the diagram may
be separated by a line, in which
dp . , • i dp
-TT- = 0, or by one in which -£•
dr\ dij
changes abruptly from a positive to
a negative value.* (In part, also,
they may be separated by an area in
which -jt- = 0.) In the representa-
tion of such cases in any diagram
of constant scale, we meet with a O
difficulty of the following nature.
Let us suppose that on the right of the line LL (fig. 10) in a volume-
entropy diagram, -J: is positive, and t>n the left negative. Then, if
we draw any circuit ABCD on the right side of LL, the direction
Fig. 10.
* The line which represents the various states of water at its maximum density for
various constant pressures is an example of the first case. A substance which as a
liquid has no proper maximum density for constant pressure, but which expands in
solidifying, affords an example of the second case.
26 GRAPHICAL METHODS IN THE
being that of the hands of a watch, the work and heat of the circuit
will be positive. But if we draw any circuit EFGH in the same
direction on the other side of the line LL, the work and heat will
be negative. For
and the direction of the circuits makes the areas positive in both
cases. Now if we should change this diagram into any diagram of
constant scale, the areas of the circuits, as representing proportionally
the work done in each case, must necessarily have opposite signs,
i.e., the direction of the circuits must be opposite. We will suppose
that the work done is positive in the diagram of constant scale, when
the direction of the circuit is that of the hands of a watch. Then, in
that diagram, the circuit ABCD would have
that direction, and the circuit EFGH the con-
trary direction, as in figure 11. Now if we
imagine an indefinite number of circuits on
each side of LL in the volume-entropy dia-
gram, it will be evident that to transform
such a diagram into one of constant scale, so
as to change the direction of all the circuits
on one side of LL, and of none on the other
the diagram must be folded over along that
line ; so that the points on one side of LL in
a diagram of constant scale do not represent
v any states of the body, while on the other
side of this line, each point, for a certain
distance at least, represents two different states of the body, which in
the volume-entropy diagram are represented by points on opposite
sides of the line LL. We have thus in a part of the field two diagrams
superposed, which must be carefully distinguished. If this be done,
as by the help of different colors, or of continuous and dotted lines,
or otherwise, and it is remembered that there is no continuity between
these superposed diagrams, except along the bounding line LL, all the
general theorems which have been developed in this article can be
readily applied to the diagram. But to the eye or to the imagination,
the figure will necessarily be much more confusing than a volume-
entropy diagram.
dt)
If -7 =0 for the line LL, there will be another inconvenience in
the use of any diagram of constant scale, viz : in the vicinity of the
line LL, -g-, i.e., l + yv>1l will have a very small value, so that areas
will be very greatly reduced in the diagram of constant scale, as com-
THERMODYNAMICS OF FLUIDS.
27
•c
3
•
1
a
0
M
Fig. 12.
pared with the corresponding areas in the volume-entropy diagram.
Therefore, in the former diagram, either the isometrics, or the isen-
tropics, or both, will be crowded together in the vicinity of the line
LL, so that this part of the diagram will be necessarily indistinct.
It may occur, however, in the volume-entropy diagram, that the
same point must represent two different states of the body. This
occurs in the case of liquids which can be vaporized. Let MM (fig. 12)
be the line representing the states of the liquid
bordering upon vaporization. This line will be * M
near to the axis of entropy, and nearly parallel
to it. If the body is in a state represented by
a point of the line MM, and is compressed
without addition or subtraction of heat, it will
remain of course liquid. Hence, the points of
the space immediately on the left of MM re-
present simple liquid. On the other hand, the
body being in the original state, if its volume
should be increased without addition or sub-
traction of heat, and if the conditions necessary
for vaporization are present (conditions relative
to the body enclosing the liquid in question,
etc.), the liquid will become partially vaporized,
but if these conditions are not present, it will continue liquid. Hence,
every point on the right of MM and sufficiently near to it represents
two different states of the body, in one of which it is partially
vaporized, and in the other it is entirely liquid. If we take the
points as representing the mixture of vapor and liquid, they form
one diagram, and if we take them as representing simple liquid, they
form a totally different diagram superposed on the first. There is
evidently no continuity between these diagrams except at the line
MM ; we may regard them as upon separate sheets united only along
MM. For the body cannot pass from the state of partial vaporization
to the state of liquid except at this line. The reverse process is
indeed possible; the body can pass from the state of superheated
liquid to that of partial vaporization, if the conditions of vaporization
alluded to above are supplied, or if the increase of volume is carried
beyond a certain limit, but not by gradual changes or reversible
processes. After such a change, the point representing the state of
the body will be found in a different position from that which it
occupied before, but the change of state cannot be properly repre-
sented by any path, as during the change the body does not satisfy
that condition of uniform temperature and pressure which has been
assumed throughout this article, and which is necessary for the
graphical methods under discussion. (See note on page 1.)
28 GRAPHICAL METHODS IN THE
Of the two superposed diagrams, that which represents simple
liquid is a continuation of the diagram on the left of MM. The
isopiestics, isothermals and isodynamics pass from one to the other
without abrupt change of direction or curvature. But that which
represents a mixture of vapor and liquid will be different in its
character, and its isopiestics and isothermals will make angles in
general with the corresponding lines in the diagram of simple liquid.
The isodynamics of the diagram of the mixture, and those of the
diagram of simple liquid, will differ in general in curvature at the
fj C ft C
line MM, but not in direction, for -,-= — p and -j- = t.
dv dr\
The case is essentially the same with some substances, as water,
for example, about the line which separates the simple liquid from a
mixture of liquid and solid.
In these cases the inconvenience of having one diagram superposed
upon another cannot be obviated by any change of the principle on
which the diagram is based. For no distortion can bring the three
sheets, which are united along the line MM (one on the left and two
on the right), into a single plane surface without superposition. Such
cases, therefore, are radically distinguished from those in which the
superposition is caused by an unsuitable method of representation.
To find the character of a volume-entropy diagram of a perfect gas,
we may make e constant in equation (D) on page 13, which will give
for the equation of an isodynamic and isothermal
r\ — a log v + Const.,
4
and we may make p constant in equation (G), which will give for the
equation of an isopiestic
r\ = (a -h c) log v + Const.
It will be observed that all the isodynamics and isothermals can be
drawn by a single pattern and so also with the isopiestics.
The case will be nearly the same with vapors in a part of the
diagram. In that part of the diagram which represents a mixture of
liquid and vapor, the isothermals, which of course are identical with
the isopiestics, are straight lines. For when a body is vaporized
under constant pressure and temperature, the quantities of heat
received are proportional to the increments of volume ; therefore, the
increments of entropy are proportional to the increments of volume.
As -j-= —p and -j-=t, any isothermal is cut at the same angle by
all the isodynamics, and is divided into equal segments by equi-
different isodynamics. The latter property is useful in drawing
systems of equidifferent isodynamics.
THERMODYNAMICS OF FLUIDS. 29
Arrangement of the Isometric, Isopiestic, Isothermal and
Isentropic about a Point.
The arrangement of the isometric, the isopiestic, the isothermal and
the isentropic drawn through any same point, in respect to the order
in which they succeed one another around that point, and in respect
to the sides of these lines toward which the volume, pressure, tem-
perature and entropy increase, is not altered by any deformation of
the surface on which the diagram is drawn, and is therefore inde-
pendent of the method by which the diagram is formed.* This
arrangement is determined by certain of the most characteristic
thermodynamic properties of the body in the state in question, and
serves in turn to indicate these properties. It is determined, namely,
by the value of f -J- J as positive, negative, or zero, i.e., by the effect
of heat as increasing or diminishing the pressure when the volume
is maintained constant, and by the nature of the internal thermo-
dynamic equilibrium of the body as stable or neutral, — an unstable
equilibrium, except as a matter of speculation, is of course out of
the question.
Let us first examine the case in which ( ~- ) is positive and the
/d \
equilibrium is stable. As - does not vanish at the point in
question, there is a definite isopiestic passing through that point,
on one side of which the pressures are greater, and on the other less,
than on the line itself. As f -?- ) = — ( -r- ) , the case is the same
\c*v/, \dr]/v
with the isothermal. It will be convenient to distinguish the sides
of the isometric, isopiestic, etc., on which the volume, pressure, etc.,
increase, as the positive sides of these lines. The condition of stability
requires that, when the pressure is constant, the temperature shall
increase with the heat received, — therefore with the entropy. This
may be written [dt : drj]p > O.f It also requires that, when there
is no transmission of heat, the pressure should increase as the volume
diminishes, i.e., that [dp : dv]^ < 0. Through the point in question,
* It is here assumed that, in the vicinity of the point in question, each point in the
diagram represents only one state of the body. The propositions developed in the fol-
lowing pages cannot be applied to points of the line where two superposed diagrams
are united (see pages 25-28) without certain modifications.
t As the notation — is used to denote the limit of the ratio of dt to d-rj, it would not
97 /dt\
be quite accurate to say that the condition of stability requires that ( — ) >0. This
\drjjp
condition requires that the ratio of the differences of temperature and entropy between
the point in question and any other infinitely near to it and upon the same isopiestic
should be positive. It is not necessary that the limit of this ratio should be positive.
30
GRAPHICAL METHODS IN THE
A (fig. 13), let there be drawn the isometric vv' and the isentropic
r\i\ ', and let the positive sides of these lines be indicated as in the
figure. The conditions (-£•) > 0 and [dp : dv]^ < 0 require that the
pressure at v and at r\ shall be greater than at A, and hence, that
the isopiestic shall fall as pp' in the figure, and have its positive side
turned as indicated. Again, the conditions (-T-) <0 and [dt : dt]]p>0
require that the temperature at ?/ and at p shall be greater than at A,
and hence, that the isothermal shall fall as tt' and have its positive
side turned as indicated. As it is not necessary that f-y-J >0, the
lines pp' and tt' may be tangent to one another at A, provided that
they cross one another, so as to have the same order about the point
A as is represented in the figure ; i.e., they may have a contact of the
second (or any even) order.* But the condition that (-^-) >0, and
\dr]/v
hence ( -7- ) < 0, does not allow pp' to be tangent to vv', nor tt' to r\r\ ' .
If f -^- J be still positive, but the equilibrium be neutral, it will be
possible for the body to change its
state without change either of tem-
perature or of pressure ; i.e., the
t' isothermal and isopiestic will be
identical. The lines will fall as in
figure 13, except that the isothermal
and isopiestic will be superposed.
I?) < °> it may
t -
Fig. 13.
In like manner, if
be proved that the lines will fall as
in figure 14 for stable equilibrium,
and in the same way for neutral
equilibrium, except that pp' and tt' will be superposed.!
*An example of this is doubtless to be found at the critical point of a fluid. See
Dr. Andrews "On the continuity of the gaseous and liquid states of matter." Phil.
Trans., vol. 159, p. 575.
If the isothermal and isopiestic have a simple tangency at A, on one side of that
point they will have such directions as will express an unstable equilibrium. A line
drawn through all such points in the diagram will form a boundary to the possible part
of the diagram. It may be that the part of the diagram of a fluid, which represents
the superheated liquid state, is bounded on one side by such a line.
i When it is said that the arrangement of the lines in the diagram must be like that
in figure 13 or in figure 14, it is not meant to exclude the case in which the figure
(13 or 14) must be turned over, in order to correspond with the diagram. In the case,
however, of diagrams formed by any of the methods mentioned in this article, if the
THERMODYNAMICS OF FLUIDS. 31
The case that (-r?) =0 includes a considerable number of con-
\dri) v
ceivable cases, which would require to be distinguished. It will be
sufficient to mention those most likely to occur.
In a field of stable equilibrium it may occur that f -f-) = Q along a
line, on one side of which (^- ) > 0, and on the other side (•?•) < 0.
\drj/v \dq/v
At any point in such a line the isopiestics will be tangent to the
isometrics and the isothermals to the isen-
tropics. (See, however, note on page 29.)
In a field of neutral equilibrium repre-
senting a mixture of two different states
of the substance, where the isothermals and
isopiestics are identical, a line may occur
which has the threefold character of an
isometric, an isothermal and an isopiestic.
For such a line (¥) = 0. If ^ has
\dri/v \dri/v
opposite signs on opposite sides of this
line, it will be an isothermal of maximum or minimum temperature.*
The case in which the body is partly solid, partly liquid and partly
vapor has already been sufficiently discussed. (See pages 23, 24.)
The arrangement of the isometric, isopiestic, etc., as given in figure
13, will indicate directly the sign of any differential co-efficient of the
form ( -J— ) , where u, w and z may be any of the quantities v, p, t, i\
\dw/z
(and e, if the isodynamic be added in the figure). The value of such
a differential co-efficient will be indicated, when the rates of increase
of v, p, etc., are indicated, as by isometrics, etc., drawn both for the
values of v, etc., at the point A, and for values differing from these by
a small quantity. For example, the value of - will be indicated
by the ratio of the segments intercepted upon an isentropic by a pair
of isometrics and a pair of isopiestics, of which the differences of
volume and pressure have the same numerical value. The case in
which W or H appears in the numerator or denominator instead of a
directions of the axes be such as we have assumed, the agreement with figure 13 will
be without inversion, and the agreement with fig. 14 will also be without inversion for
volume-entropy diagrams, but with inversion for volume-pressure or entropy-temperature
diagrams, or those in which a;=logv and y = logp, or x = i) and y=logt.
*As some liquids expand and others contract in solidifying, it is possible that there
are some which will solidify either with expansion, or without change of volume, or
with contraction, according to the pressure. If any such there are, they afford examples
of the case mentioned above.
32 THERMODYNAMICS OF FLUIDS.
function of the state of the body, can be reduced to the preceding by
the substitution of pdv for dW, or that of tdrj for dH.
In the foregoing discussion, the equations which express the funda-
mental principles of thermodynamics in an analytical form have been
assumed, and the aim has only been to show how the same relations
may be expressed geometrically. It would, however, be easy, starting
from the first and second laws of thermodynamics as usually enun-
ciated, to arrive at the same results without the aid of analytical
formulae, — to arrive, for example, at the conception of energy, of
entropy, of absolute temperature, in the construction of the diagram
without the analytical definitions of these quantities, and to obtain the
various properties of the diagram without the analytical expression
of the thermodynamic properties which they involve. Such a course
would have been better fitted to show the independence and sufficiency
of a graphical method, but perhaps less suitable for an examination
of the comparative advantages or disadvantages of different graphical
methods.
The possibility of treating the thermodynamics of fluids by such
graphical methods as have been described evidently arises from the
fact that the state of the body considered, like the position of a point
in a plane, is capable of two and only two independent variations.
It is, perhaps, worthy of notice, that when the diagram is only used
to demonstrate or illustrate general theorems, it is not necessary,
although it may be convenient, to assume any particular method of
forming the diagram ; it is enough to suppose the different stages of
the body to be represented continuously by points upon a sheet.
II.
A METHOD OF GEOMETRICAL REPRESENTATION OF THE
THERMODYNAMIC PROPERTIES OF SUBSTANCES BY
MEANS OF SURFACES.
[Transactions of the Connecticut Academy, II. pp. 382-404, Dec. 1873.]
THE leading thermodynamic properties of a fluid are determined
by the relations which exist between the volume, pressure, tempera-
ture, energy, and entropy of a given mass of the fluid in a state of
thermodynamic equilibrium. The same is true of a solid in regard
to those properties which it exhibits in processes in which the
pressure is the same in every direction about any point of the solid.
But all the relations existing between these five quantities for any
substance (three independent relations) may be deduced from the
single relation existing for that substance between the volume, energy,
and entropy. This may be done by means of the general equation,
de — tdri—pdv, (1)*
that is, *--l£)» (2)
where v, p, t, e, and 77 denote severally the volume, pressure, absolute
temperature, energy, and entropy of the body considered. The sub-
script letter after the differential coefficient indicates the quantity
which is supposed constant in the differentiation.
Representation of Volume, Entropy, Energy, Pressure, and
Temperature.
Now the relation between the volume, entropy, and energy may
be represented by a surface, most simply if the rectangular co-
ordinates of the various points of the surface are made equal to the
volume, entropy, and energy of the body in its various states. It
may be interesting to examine the properties of such a surface, which
*For the demonstration of this equation, and in regard to the units used in the
measurement of the quantities, the reader is referred to page 2.
G. I. C
34 KEPRESENTATION BY SURFACES OF THE
we will call the thermodynamic surface of the body for which it i»
formed.*
To fix our ideas, let the axes of v, rj, and e have the directions
usually given to the axes of X, Y, and Z (v increasing to the right,
tj forward, and e upward). Then the pressure and temperature of
the state represented by any point of the surface are equal to the
tangents of the inclinations of the surface to the horizon at that
point, as measured in planes perpendicular to the axes of r\ and of v
respectively. (Eqs. 2 and 3.) It must be observed, however, that
in the first case the angle of inclination is measured upward from
the direction of decreasing v, and in the second, upward from the
direction of increasing tj. Hence, the tangent plane at any point
indicates the temperature and pressure of the state represented. It
will be convenient to speak of a plane as representing a certain
pressure and temperature, when the tangents of its inclinations to
the horizon, measured as above, are equal to that pressure and
temperature.
Before proceeding farther, it may be worth while to distinguish
between what is essential and what is arbitrary in a surface thus
formed. The position of the plane v = Q in the surface is evidently
fixed, but the position of the planes ij = 0, e = 0 is arbitrary, provided
the direction of the axes of r\ and e be not altered. This results from
the nature of the definitions of entropy and energy, which involve
each an arbitrary constant. As we may make r\ — 0 and e = 0 for any
state of the body which we may choose, we may place the origin of
co-ordinates at any point in the plane v = 0. Again, it is evident
from the form of equation (1) that whatever changes we may make in
the units in which volume, entropy, and energy are measured, it will
always be possible to make such changes in the units of temperature
and pressure, that the equation will hold true in its present form,
without the introduction of constants. It is easy to see how a change
of the units of volume, entropy, and energy would affect the surface.
The projections parallel to any one of the axes of distances between
points of the surface would be changed in the ratio inverse to that
in which the corresponding unit had been changed. These con-
siderations enable us to foresee to a certain extent the nature of the
general properties of the surface which we are to investigate. They
* Professor J. Thomson has proposed and used a surface in which the co-ordinates
are proportional to the volume, pressure, and temperature of the body. (Proc. Roy.
Soc., Nov. 16, 1871, vol. xx, p. 1 ; and Phil. Mag., vol. xliii, p. 227.) It is evident,
however, that the relation between the volume, pressure, and temperature affords a
less complete knowledge of the properties of the body than the relation between the
volume, entropy, and energy. For, while the former relation is entirely determined by
the latter, and can be derived from it by differentiation, the latter relation is by no
means determined by the former.
THERMODYNAMIC PROPERTIES OF SUBSTANCES. 35
must be such, namely, as shall not be affected by any of the changes
mentioned above. For example, we may find properties which concern
the plane v = 0 (as that the whole surface must necessarily fall on the
positive side of this plane), but we must not expect to find properties
which concern the planes ij = 0, or e = 0, in distinction from others
parallel to them. It may be added that, as the volume, entropy, and
energy of a body are equal to the sums of the volumes, entropies, and
energies of its parts, if the surface should be constructed for bodies
differing in quantity but not in kind of matter, the different surfaces
thus formed would be similar to one another, their linear dimensions
being proportional to the quantities of matter.
Nature of that Part of the Surface which represents States which are
not Homogeneous.
This mode of representation of the volume, entropy, energy, pressure,
and temperature of a body will apply as well to the case in which
different portions of the body are in different states (supposing always
that the whole is in a state of thermodynamic equilibrium), as to that
in which the body is uniform in state throughout. For the body
taken as a whole has a definite volume, entropy, and energy, as well
as pressure and temperature, and the validity of the general equation
(1) is independent of the uniformity or diversity in respect to state
of the different portions of the body.* It is evident, therefore, that
*It is, however, supposed in this equation that the variations in the state of the
body, to which dv, dy, and rfe refer, are such as may be produced reversibly by expan-
sion and compression or by addition and subtraction of heat. Hence, when the body
consists of parts in different states, it is necessary that these states should be such as
can pass either into the other without sensible change of pressure or temperature.
Otherwise, it would be necessary to suppose in the differential equation (1) that the
proportion in which the body is divided into the different states remains constant.
But such a limitation would render the equation as applied to a compound of different
states valueless for our present purpose. If, however, we leave out of account the
cases in which we regard the states as chemically different from one another, which
lie beyond the scope of this paper, experience justifies us in assuming the above con-
dition (that either of the two states existing in contact can pass into the other without
sensible change of the pressure or temperature), as at least approximately true, when
one of the states is fluid. But if both are solid, the necessary mobility of the parts is
wanting. It must therefore be understood, that the following discussion of the com-
pound states is not intended to apply without limitation to the exceptional cases, where
we have two different solid states of the same substance at the same pressure and
temperature. It may be added that the thermodynamic equilibrium which subsists
between two such solid states of the same substance differs from that which subsists
when one of the states is fluid, very much as in statics an equilibrium which is main-
tained by friction differs from that of a frictionless machine in which the active forces
are so balanced, that the slightest change of force will produce motion in either
direction.
Another limitation is rendered necessary by the fact that in the following discussion
the magnitude and form of the bounding and dividing surfaces are left out of account ;
36 REPRESENTATION BY SURFACES OF THE
the thermodynamic surface, for many substances at least, can be
divided into two parts, of which one represents the homogeneous
states, the other those which are not so. We shall see that, when
the former part of the surface is given, the latter can readily be
formed, as indeed we might expect. We may therefore call the
former part the primitive surface, and the latter the derived surface.
To ascertain the nature of the derived surface and its relations to
the primitive surface sufficiently to construct it when the latter is
given, it is only necessary to use the principle that the volume,
entropy, and energy of the whole body are equal to the sums of the
volumes, entropies, and energies respectively of the parts, while the
pressure and temperature of the whole are the same as those of each
of the parts. Let us commence with the case in which the body is
in part solid, in part liquid, and in part vapor. The position of the
point determined by the volume, entropy, and energy of such a com-
pound will be that of the center of gravity of masses proportioned
to the masses of solid, liquid, and vapor placed at the three points of
the primitive surface which represent respectively the states of com-
plete solidity, complete liquidity, and complete vaporization, each at
the temperature and pressure of the compound. Hence, the part of
the surface which represents a compound of solid, liquid, and vapor is
a plane triangle, having its vertices at the points mentioned. The
fact that the surface is here plane indicates that the pressure and
temperature are here constant, the inclination of the plane indicating
the value of these quantities. Moreover, as these values are the same
for the compound as for the three different homogeneous states cor-
responding to its different portions, the plane of the triangle is
tangent at each of its vertices to the primitive surface, viz: at one
vertex to that part of the primitive surface which represents solid, at
another to the part representing liquid, and at the third to the part
representing vapor.
When the body consists of a compound of two different homo-
geneous states, the point which represents the compound state will be
at the center of gravity of masses proportioned to the masses of the
parts of the body in the two different states and placed at the points
of the primitive surface which represent these two states (i.e., which
represent the volume, entropy, and energy of the body, if its whole
mass were supposed successively in the two homogeneous states which
occur in its parts). It will therefore be found upon the straight line
so that the results are in general strictly valid only in cases in which the influence
of these particulars may be neglected. When, therefore, two states of the substance
are spoken of as in contact, it must be understood that the surface dividing them
is plane. To consider the subject in a more general form, it would be necessary to
introduce considerations which belong to the theories of capillarity and crystallization.
THERMODYNAMIC PROPERTIES OF SUBSTANCES. 37
which unites these two points. As the pressure and temperature are
evidently constant for this line, a single plane can be tangent to the
derived surface throughput this line and at each end of the line tan-
gent to the primitive surface.* If we now imagine the temperature
and pressure of the compound to vary, the two points of the primitive
surface, the line in the derived surface uniting them, and the tangent
*It is here shown that, if two different states of the substance are such that they
can exist permanently in contact with each other, the points representing these states
in the thermodynamic surface have a common tangent plane. We shall see hereafter
that the converse of this is true, — that, if two points in the thermodynamic surface have
a common tangent plane, the states represented are such as can permanently exist in
contact ; and we shall also see what determines the direction of the discontinuous
change which occurs when two different states of the same pressure and temperature,
for which the condition of a common tangent plane is not satisfied, are brought into
contact.
It is easy to express this condition analytically. Resolving it into the conditions,
that the tangent planes shall be parallel, and that they shall cut the axis of e at the
same point, we have the equations
P'=P", <«)
t' = t"t (ft)
e' - t'r,' +p'v' = e" - t"-n" +p"v", (7)
where the letters which refer to the different states are distinguished by accents. If
there are three states which can exist in contact, we must have for these states,
e' _ jy +p'v' = e" _ t"i)' ' +p"
These results are interesting, as they show us how we might foresee whether two
given states of a substance of the same pressure and temperature, can or cannot exist
in contact. It is indeed true, that the values of e and t\ cannot like those of v, p, and t
be ascertained by mere measurements upon the substance while in the two states in
question. It is necessary, in order to find the value of e" - e' or t\" - if, to carry out
measurements upon a process by which the substance is brought from one state to the
other, but this need not be by a process in which the two given states shall be found in con-
tact, and in some cases at least it may be done by processes in which the body remains
always homogeneous in state. For we know by the experiments of Dr. Andrews,
Phil. Trans., vol. 159, p. 575, that carbonic acid may be carried from any of the
states which we usually call liquid to any of those which we usually call gas, without
losing its homogeneity. Now, if we had so carried it from a state of liquidity to a
state of gas of the same pressure and temperature, making the proper measurements
in the process, we should be able to foretell what would occur if these two states of
the substance should be brought together, — whether evaporation would take place, or
condensation, or whether they would remain unchanged in contact, — although we had
never seen the phenomenon of the coexistence of these two states, or of any other two
states of this substance.
Equation (7) may be put in a form in which its validity is at once manifest for two
states which can pass either into the other at a constant pressure and temperature.
If we put p' and t' for the equivalent p" and £", the equation may be written
Here the left hand member of the equation represents the difference of energy in the
two states, and the two terms on the right represent severally the heat received and
38 REPRESENTATION BY SURFACES OF THE
plane will change their positions, maintaining the aforesaid relations.
We may conceive of the motion of the tangent plane as produced by
rolling upon the primitive surface, while tangent to it in two points,
and as it is also tangent to the derived surface in the lines joining
these points, it is evident that the latter is a developable surface
and forms a part of the envelop of the successive positions of the
rolling plane. We shall see hereafter that the form of the primitive
surface is such that the double tangent plane does not cut it, so
that this rolling is physically possible.
From these relations may be deduced by simple geometrical
considerations one of the principal propositions in regard to such
compounds. Let the tangent plane touch the pri-
mitive surface at the two points L and V (fig. 1),
which, to fix our ideas, we may suppose to repre-
sent liquid and vapor; let planes pass through
these points perpendicular to the axes of v and r\
v respectively, intersecting in the line AB, which
will be parallel to the axis of e. Let the tangent
plane cut this line at A, and let LB and VC be
drawn at right angles to AB and parallel to the
axes of rj and v. Now the pressure and temperature represented by
AC AB
the tangent plane are evidently p^ and ^- respectively, and if we
suppose the tangent plane in rolling upon the primitive surface to
turn about its instantaneous axis LV an infinitely small angle, so
AA' AA'
as to meet AB in A7, dp and dt will be equal to
respectively. Therefore,
dt~CV~v"-v"
where i/ and rf denote the volume and entropy for the point L,
and v" and if those for the point V. If we substitute for rf — rj
T
its equivalent - (r denoting the heat of vaporization), we have the
c
equation in its usual form, -77 = ^—* K-
dt t(v — v)
the work done when the body passes from one state to the other. The equation may
also be derived at once from the general equation (1) by integration.
It is well known that when the two states being both fluid meet in a curved surface,
/ 1 1\
instead of (a) we have p"-p'= T ( - + ~. ) ,
\r r J
where r and / are the radii of the principal curvatures of the surface of contact at any
point (positive, if the concavity is toward the mass to which p" refers), and T is what
is called the superficial tension. Equation (£), however, holds good for such cases, and
it might easily be proved that the same is true of equation (7). In other words, the
tangent planes for the points in the thermodynamic surface representing the two states
cut the plane v=0 in the same line.
THERMODYNAMIC PROPERTIES OF SUBSTANCES. 39
Properties of the Surface relating to Stability of Thermodynamic
Equilibrium.
We will now turn our attention to the geometrical properties of
the surface, which indicate whether the thermodynamic equilibrium
of the body is stable, unstable, or neutral. This will involve the
consideration, to a certain extent, of the nature of the processes which
take place when equilibrium does not subsist. We will suppose the
body placed in a medium of constant pressure and temperature ; but
as, when the pressure or temperature of the body at its surface differs
from that of the medium, the immediate contact .of the two is hardly
consistent with the continuance of the initial pressure and temperature
of the medium, both of which we desire to suppose constant, we will
suppose the body separated from the medium by an envelop which
will yield to the smallest differences of pressure between the two, but
which can only yield very gradually, and which is also a very poor
conductor of heat. It will be convenient and allowable for the pur-
poses of reasoning to limit its properties to those mentioned, and to
suppose that it does not occupy any space, or absorb any heat except
what it transmits, i.e., to make its volume and its specific heat 0. By
the intervention of such an envelop, we may suppose the action of the
body upon the medium to be so retarded as not sensibly to disturb
the uniformity of pressure and temperature in the latter.
When the body is not in a state of thermodynamic equilibrium, its
state is not one of those which are represented by our surface. The
body, however, as a whole has a certain volume, entropy, and energy,
which are equal to the sums of the volumes, etc., of its parts.* If,
then, we suppose points endowed with mass proportional to the
masses of the various parts of the body, which are in different thermo-
dynamic states, placed in the positions determined by the states
and motions of these parts, (i.e., so placed that their co-ordinates are
equal to the volume, entropy, and energy of the whole body supposed
successively in the same states and endowed with the same velocities
as the different parts), the center of gravity of such points thus
placed will evidently represent by its co-ordinates the volume, entropy,
and energy of the whole body. If all parts of the body are at rest,
the point representing its volume, entropy, and energy will be the
center of gravity of a number of points upon the primitive surface.
The effect of motion in the parts of the body will be to move the
corresponding points parallel to the axis of e, a distance equal in
each case to the vis viva of th^ whole body, if endowed with the
*As the discussion is to apply to cases in which the parts of the body are in (sensible)
motion, it is necessary to define the sense in which the word energy is to be used. We
will use the word as including the vis viva of sensible motions.
40 KEPKESENTATION BY SURFACES OF THE
velocity of the part represented ; — the center of gravity of points
thus determined will give the volume, entropy, and energy of the
whole body.
Now let us suppose that the body having the initial volume,
entropy, and energy, v, r(, and e', is placed (enclosed in an envelop as
aforesaid) in a medium having the constant pressure P and tempera-
ture T, and by the action of the medium and the interaction of its
own parts comes to a final state of rest in which its volume, etc., are
v", rf\ e" ; — we wish to find a relation between these quantities. If
we regard, as we may, the medium as a very large body, so that
imparting heat to it or compressing it within moderate limits will
have no appreciable effect upon its pressure and temperature, and
write V, H, and E, for its volume, entropy, and energy, equation (1)
becomes dE=TdH-PdV,
which we may integrate regarding P and T as constants, obtaining
E"-E' = TH"-TH'-PV"+PV'y (a)
where E', E", etc., refer to the initial and final states of the medium.
Again, as the sum of the energies of the body and the surrounding
medium may become less, but cannot become greater (this arises from
the nature of the envelop supposed), we have
e"+E"^e'+E'. (b)
Again as the sum of the entropies may increase but cannot dimmish
ri' + H"^ri + H'. (c)
Lastly, it is evident that
V"+F"=?/+F'. (d)
These four equations may be arranged with slight changes as follows :
-E"+TH"-PV"= -E'+TH'-PV
- Tn" - TH" ^ - 2V - TH'
Pv"+PV" = Pv'+PV.
By addition we have
e" _ zy ' + pv» < e' _ Tff + Pv'. (e}
Now the two members of this equation evidently denote the vertical
distances of the points (v", r[f, e") and (v', rf, e') above the plane pass-
ing through the origin and representing the pressure P and tempera-
ture T. And the equation expresses that the ultimate distance is less
or at most equal to the initial. It is evidently immaterial whether
the distances be measured vertically or normally, or that the fixed
plane representing P and T should pass through the origin; but
distances must be considered negative when measured from a point
below the plane.
THERMODYNAMIC PROPERTIES OF SUBSTANCES. 41
It is evident that the sign of inequality holds in (e) if it holds in
either (6) or (c), therefore, it holds in (e) if there are any differences
of pressure or temperature between the different parts of the body
or between the body and the medium, or if any part of the body has
sensible motion. (In the latter case, there would be an increase of
entropy due to the conversion of this motion into heat.) But even if
the body is initially without sensible motion and has throughout the
same pressure and temperature as the medium, the sign < will still
hold if different parts of the body are in states represented by points
in the thermodynamic surface at different distances from the fixed
plane representing P and T. For it certainly holds if such initial
circumstances are followed by differences of pressure or temperature,
or by sensible velocities. Again, the sign of inequality would neces-
sarily hold if one part of the body should pass, without producing
changes of pressure or temperature or sensible velocities, into the
state of another part represented by a point not at the same distance
from the fixed plane representing P and T. But these are the only
suppositions possible in the case, unless we suppose that equilibrium
subsists, which would require that the points in question should have
a common tangent plane (page 37), whereas by supposition the planes
tangent at the different points are parallel but not identical.
The results of the preceding paragraph may be summed up as
follows: — Unless the body is initially without sensible motion, and
its state, if homogeneous, is such as is represented by a point in the
primitive surface where the tangent plane is parallel to the fixed plane
representing P and T, or, if the body is not homogeneous in state,
unless the points in the primitive surface representing the states of
its parts have a common tangent plane parallel to the fixed plane
representing P and T, such changes will ensue that the distance
of the point representing the volume, entropy, and energy of the
body from that fixed plane will be diminished (distances being con-
sidered negative if measured from points beneath the plane). Let
us apply this result to the question of the stability of the body when
surrounded, as supposed, by a medium of constant temperature and
pressure.
The state of the body in equilibrium will be represented by a point
in the thermodynamic surface, and as the pressure and temperature of
the body are the same as those of the surrounding medium, we may
take the tangent plane at that point as the fixed plane representing
P and T. If the body is not homogeneous in state, although in
equilibrium, we may, for the purposes of this discussion of stability,
either take a point in the derived surface as representing its state, or
we may take the points in the primitive surface which represent the
states of the different parts of the body. These points, as we have
42 REPEESENTATION BY SURFACES OF THE
seen (page 37), have a common tangent plane, which is identical with
the tangent plane for the point in the derived surface.
Now, if the form of the surface be such that it falls above the tan-
gent plane except at the single point of contact, the equilibrium is
necessarily stable ; for if the condition of the body be slightly altered,
either by imparting sensible motion to any part of the body, or by
slightly changing the state of any part, or by bringing any small
part into any other thermodynamic state whatever, or in all of these
ways, the point representing the volume, entropy, and energy of the
whole body will then occupy a position above the original tangent
plane, and the proposition above enunciated shows that processes
will ensue which will diminish the distance of this point from that
plane, and that such processes cannot cease until the body is brought
back into its original condition, when they will necessarily cease on
account of the form supposed of the surface.
On the other hand, if the surface have such a form that any part
of it falls below the fixed tangent plane, the equilibrium will be
unstable. For it will evidently be possible by a slight change in the
original condition of the body (that of equilibrium with the surround-
ing medium and represented by the point or points of contact) to
bring the point representing the volume, entropy, and energy of the
body into a position below the fixed tangent plane, in which case we
see by the above proposition that processes will occur which will
carry the point still farther from the plane, and that such processes
cannot cease until all the body has passed into some state entirely
different from its original state.
It remains to consider the case in which the surface, although it
does not anywhere fall below the fixed tangent plane, nevertheless
meets the plane in more than one point. The equilibrium in this
case, as we might anticipate from its intermediate character between
the cases already considered, is neutral. For if any part of the
body be changed from its original state into that represented by
another point in the thermodynamic surface lying in the same tan-
gent plane, equilibrium will still subsist. For the supposition in
regard to the form of the surface implies that uniformity in tempera-
ture and pressure still subsists, nor can the body have any necessary
tendency to pass entirely into the second state or to return into the
original state, for a change of the values of T and P less than any
assignable quantity would evidently be sufficient to reverse such a
tendency if any such existed, as either point at will could by such an
infinitesimal variation of T and P be made the nearer to the plane
representing T and P.
It must be observed that in the case where the thermodynamic
surface at a certain point is concave upward in both its principal
THERMODYNAMIC PROPERTIES OF SUBSTANCES. 43
curvatures, but somewhere falls below the tangent plane drawn
through that point, the equilibrium although unstable in regard to
discontinuous changes of state is stable in regard to continuous
changes, as appears on restricting the test of stability to the vicinity
of the point in question ; that is, if we suppose a body to be in a state
represented by such a point, although the equilibrium would show
itself unstable if we should introduce into the body a small portion
of the same substance in one of the states represented by points
below the tangent plane, yet if the conditions necessary for such a
discontinuous change are not present, the equilibrium would be
stable. A familiar example of this is afforded by liquid water when
heated at any pressure above the temperature of boiling water at
that pressure.*
Leading Features of the Thermodynamic Surface for Substances
which take the forms of Solid, Liquid, and Vapor.
We are now prepared to form an idea of the general character of
the primitive and derived surfaces and their mutual relations for a
substance which takes the forms of solid, liquid, and vapor. The
primitive surface will have a triple tangent plane touching it at the
three points which represent the three states which can exist in
contact. Except at these three points, the primitive surface falls
entirely above the tangent plane. That part of the plane which forms
a triangle having its vertices at the three points of contact, is the
derived surface which represents a compound of the three states of the
substance. We may now suppose the plane to roll on the under side
of the surface, continuing to touch it in two points without cutting it.
This it may do in three ways, viz : it may commence by turning about
any one of the sides of the triangle aforesaid. Any pair of points
which the plane touches at once represent states which can exist
permanently in contact. In this way six lines are traced upon the
surface. These lines have in general a common property, that a
tangent plane at any point in them will also touch the surface in
another point. We must say in general, for, as we shall see hereafter,
this statement does not hold good for the critical point. A tangent
plane at any point of the surface outside of these lines has the surface
*If we wish to express in a single equation the necessary and sufficient condition
of thermodynamic equilibrium for a substance when surrounded by a medium of constant
pressure P and temperature T, this equation may be written
when 5 refers to the variation produced by any variations in the state of the parts of
the body, and (when different parts of the body are in different states) in the proportion
in which the body is divided between the different states. The condition of stable
equilibrium is that the value of the expression in the parenthesis shall be a minimum.
44
REPRESENTATION BY SURFACES OF THE
entirely above it, except the single point of contact. A tangent plane
at any point of the primitive surface within these lines will cut the
surface. These lines, therefore, taken together may be called the
limit of absolute stability, and the surface outside of them, the surface
of absolute stability. That part of the envelop of the rolling plane,
which lies between the pair of lines which the plane traces on the
surface, is a part of the derived surface, and represents a mixture of
two states of the substance.
The relations of these lines and surfaces are roughly represented in
horizontal projection* in figure 2, in which the full lines represent lines
on the primitive surface, and the dotted lines those on the derived
surface. S, L, and V are the points which have a common tangent
Fig. 2.
plane and represent the states of solid, liquid, and vapor which can
exist in contact. The plane triangle SLV is the derived surface
representing compounds of these states. LL' and VV are the pair of
lines traced by the rolling double tangent plane, between which lies
the derived surface representing compounds of liquid and vapor.
VV" and SS" are another such pair, between which lies the derived
surface representing compounds of vapor and solid. SS'" and LI/"
are the third pair, between which lies the derived surface representing
a compound of solid and liquid. L"'LL', V'VV" and S"SS"' are the
boundaries of the surfaces which represent respectively the absolutely
stable states of liquid, vapor, and solid.
The geometrical expression of the results which Dr. Andrews,
* A horizontal projection of the thermodynamic surface is identical with the diagram
described on pages 20-28 of this volume, under the name of the volume-entropy
diagram.
THEEMODYNAMIC PROPERTIES OF SUBSTANCES. 45
Phil. Trans., vol. 159, p. 575, has obtained by his experiments with
carbonic acid is that, in the case of this substance at least, the derived
surface which represents a compound of liquid and vapor is terminated
as follows : as the tangent plane rolls upon the primitive surface,
the two points of contact approach one another and finally fall
together. The rolling of the double tangent plane necessarily comes
to an end. The point where the two points of contact fall together is
the critical point. Before considering farther the geometrical character-
istics of this point and their physical significance, it will be convenient
to investigate the nature of the primitive surface which lies between
the lines which form the limit of absolute stability.
Between two points of the primitive surface which have a common
tangent plane, as those represented by L' and V in figure 2, if there
is no gap in the primitive surface, there must evidently be a region
where the surface is concave toward the tangent plane in one of its
principal curvatures at least, and therefore represents states of un-
stable equilibrium in respect to continuous as well as discontinuous
changes (see pages 42, 43).* If we draw a line upon the primitive
surface, dividing it into parts which represent respectively stable and
unstable equilibrium, in respect to continuous changes, i.e., dividing
the surface which is concave upward in both its principal curvatures
from that which is concave downward in one or both, this line, which
may be called the limit of essential instability, must have a form
somewhat like that represented by ll'Cvv'ss' in figure 2. It touches
the limit of absolute stability at the critical point C. For we may
take a pair of points in LC and VC having a common tangent plane
as near to C as we choose, and the line joining them upon the primi-
tive surface made by a plane section perpendicular to the tangent
plane, will pass through an area of instability.
The geometrical properties of the critical point in our surface may
be made more clear by supposing the lines of curvature drawn upon
the surface for one of the principal curvatures, that one, namely,
which has different signs upon different sides of the limit of essential
instability. The lines of curvature which meet this line will in
general cross it. At any point where they do so, as the sign of their
curvature changes, they evidently cut a plane tangent to the surface,
and therefore the surface itself cuts the tangent plane. But where
one of these lines of curvature touches the limit of essential instability
without crossing it, so that its curvature remains always positive
(curvatures being considered positive when the concavity is on the
upper side of the surface), the surface evidently does not cut the
* This is the same result as that obtained by Professor J. Thomson in connection with
the surface referred to in the note on page 34.
46 REPRESENTATION BY SURFACES OF THE
tangent plane, but has a contact of the third order with it in the section
of least curvature. The critical point, therefore, must be a point
where the line of that principal curvature which changes its sign
is tangent to the line which separates positive from negative
curvatures.
From the last paragraphs we may derive the following physical
property of the critical state : — Although this is a limiting state
between those of stability and those of instability in respect to con-
tinuous changes, and although such limiting states are in general
unstable in respect to such changes, yet the critical state is stable in
regard to them. A similar proposition is true in regard to absolute
stability, i.e., if we disregard the distinction between continuous and
discontinuous changes, viz : that although the critical state is a limit-
ing state between those of stability and instability, and although the
equilibrium of such limiting states is in general neutral (when we
suppose the substance surrounded by a medium of constant pressure
and temperature), yet the critical point is stable.
From what has been said of the curvature of the primitive surface
at the critical point, it is evident, that if we take a point in this
surface infinitely near to the critical point, and such that the tangent
planes for these two points shall intersect in a line perpendicular to
the section of least curvature at the critical point, the angle made by
the two tangent planes will be an infinitesimal of the same order as
the cube of the distance of these points. Hence, at the critical point
//72TA //72r>\ //72/\ /<72/\
(^)=0 (^)=0 ( — 1=0 ( — ]=0
1 7 9 / v-'» V 7 <>i / **J \ 7 O I VJ I 7 O I VJ
\dviJt \dr}*/t \dv*/p \drj2/p
and if we imagine the isothermal and isopiestic (line of constant
pressure) drawn for the critical point upon the primitive surface,
these lines will have a contact of the second order.
Now the elasticity of the substance at constant temperature and
its specific heat at constant pressure may be defined by the equations r
_ (dp\ _j.(dt)\
therefore at the critical point
e=0, 1 = 0,
g£\ 0> gf)=0> gi)=0> gh=a
\dv/t \dr]/t \dv/p \driJp
The last four equations would also hold good if p were substituted
for tt and vice versa.
THERMODYNAMIC PROPERTIES OF SUBSTANCES. 47
We have seen that in the case of such substances as can pass con-
tinuously from the state of liquid to that of vapor, unless the primi-
tive surface is abruptly terminated, and that in a line which passes
through the critical point, a part of it must represent states which are
essentially unstable (i.e., unstable in regard to continuous changes),
and therefore cannot exist permanently unless in very limited spaces.
It does not necessarily follow that such states cannot be realized at
all. It appears quite probable, that a substance initially in the
critical state may be allowed to expand so rapidly that, the time being
too short for appreciable conduction of heat, it will pass into some of
these states of essential instability. No other result is possible on
the supposition of no transmission of heat, which requires that the
points representing the states of all the parts of the body shall be
confined to the isentropic (adiabatic) line of the critical point upon
the primitive surface. It will be observed that there is no instability
in regard to changes of state thus limited, for this line (the plane
section of the primitive surface perpendicular to the axis of rj) is con-
cave upward, as is evident from the fact that the primitive surface
lies entirely above the tangent plane for the critical point.
We may suppose waves of compression and expansion to be propa-
gated in a substance initially in the critical state. The velocity of
propagation will depend upon the value of (-£-) , i.e., of — (-™~) •
Now for a wave of compression the value of these expressions is
determined by the form of the isentropic on the primitive surface.
If a wave of expansion has the same velocity approximately as one
of compression, it follows that the substance when expanded under
the circumstances remains in a state represented by the primitive
surface, which involves the realization of states of essential instability.
/cZ2e\
The value of (-r-») in the derived surface is. it will be observed,
Vcfor/,,
totally different from its value in the primitive surface, as the
curvature of these surfaces at the critical point is different.
The case is different in regard to the part of the surface between
the limit of absolute stability and the limit of essential instability.
Here, we have experimental knowledge of some of the states repre-
sented. In water, for example, it is well known that liquid states can
be realized beyond the limit of absolute stability, — both beyond the
part of the limit where vaporization usually commences (LI/ in figure
2), and beyond the part where congelation usually commences (LL"').
That vapor may also exist beyond the limit of absolute stability, i.e.,
that it may exist at a given temperature at pressures greater than
that of equilibrium between the vapor and its liquid meeting in a
plane surface at that temperature, the considerations adduced by Sir
48 EEPRESENTATION BY SURFACES OF THE
W. Thomson in his paper " On the equilibrium of a vapor at the
curved surface of a liquid" (Proc. Roy. Soc. Edinb., Session 1869-1870,
and Phil. Mag., vol. xlii, p. 448), leave no room for doubt. By experi-
ments like that suggested by Professor J. Thomson in his paper
already referred to, we may be able to carry vapors farther beyond
the limit of absolute stability.* As the resistance to deformation
characteristic of solids evidently tends to prevent a discontinuous
change of state from commencing within them, substances can doubt-
less exist in solid states very far beyond the limit of absolute stability.
The surface of absolute stability, together with the triangle repre-
senting a compound of three states, and the three developable surfaces
which have been described representing compounds of two states,
forms a continuous sheet, which is everywhere concave upward
except where it is plane, and has only one value of e for any given
values of v and r\. Hence, as t is necessarily positive, it has only one
value of r\ for any given values of v and e. If vaporization can take
place at every temperature except 0, p is everywhere positive, and
the surface has only one value of v for any given values of r\ and e.
It forms the surface of dissipated energy. If we consider all the
points representing the volume, entropy, and energy of the body in
every possible state, whether of equilibrium or not, these points will
form a solid figure unbounded in some directions, but bounded in
others by this surface.!
*If we experiment with a fluid which does not wet the vessel which contains it,
we may avoid the necessity of keeping the vessel hotter than the vapor, in prder to
prevent condensation. If a glass bulb with a stem of sufficient length be placed vertically
with the open end of the stem in a cup of mercury, the stem containing nothing but
mercury and its vapor, and the bulb nothing but the vapor, the height at which the
mercury rests in the stem, affords a ready and accurate means of determining the
pressure of the vapor. If the stem at the top of the column of liquid should be made
hotter than the bulb, condensation would take place in the latter, if the liquid were one
which would wet the bulb. But as this is not the case, it appears probable, that if
the experiment were conducted with proper precautions, there would be no condensa-
tion within certain limits in regard to the temperatures. If condensation should take
place, it would be easily observed, especially if the bulb were bent over, so that the
mercury condensed could not run back into the stem. So long as condensation does
not occur, it will be easy to give any desired (different) temperatures to the bulb and
the top of the column of mercury in the stem. The temperature of the latter will
determine the pressure of the vapor in the bulb. In this way, it would appear, we
may obtain in the bulb vapor of mercury having pressures greater for the tempera-
tures than those of saturated vapor.
f This description of the surface of dissipated energy is intended to apply to a sub-
stance capable of existing as solid, liquid, and vapor, and which presents no anomalies
in its thermodynamic properties. But, whatever the form of the primitive surface
may be, if we take the parts of it for every point of which the tangent plane does
not cut the primitive surface, together with all the plane and developable derived
surfaces which can be formed in a manner analogous to those described in the preceding
pages, by fixed and rolling tangent planes which do not cut the primitive surface, —
THERMODYNAMIC PROPERTIES OF SUBSTANCES. 49
The lines traced upon the primitive surface by the rolling double
tangent plane, which have been called the limit of absolute stability,
do not end at the vertices of the triangle which represents a mixture
of those states. For when the plane is tangent to the primitive surface
in these three points, it can commence to roll upon the surface as
a double tangent plane not only by leaving the surface at one of
these points, but also by a rotation in the opposite direction. In the
latter case, however, the lines traced upon the primitive surface by
the points of contact, although a continuation of the lines previously
described, do not form any part of the limit of absolute stability.
And the parts of the envelops of the rolling plane between these lines,
although a continuation of the developable surfaces which have been
described, and representing states of the body, of which some at least
may be realized, are of minor interest, as they form no part of the
surface of dissipated energy on the one hand, nor have the theoretical
interest of the primitive surface on the other.
Problems relating to the Surface of Dissipated Energy.
The surface of dissipated energy has an important application to a
certain class of problems which refer to the results which are theo-
retically possible with a given body or system of bodies in a given
initial condition.
For example, let it be required to find the greatest amount of
mechanical work which can be obtained from a given quantity of a
certain substance in a given initial state, without increasing its total
volume or allowing heat to pass to or from external bodies, except
such surfaces taken together will form a continuous sheet, which, if we reject the
part, if any, for which p < 0, forms the surface of dissipated energy and has the geo-
metrical properties mentioned above.
There will, however, be no such part in which ^><0, if there is any assignable
temperature t' at which the substance has the properties of a perfect gas except when its
volume is less than a certain quantity v'. For the equations of an isothermal line in the
thermodynamic surface of a perfect gas are (see equations (B) and (E) on pages 12-13)
The isothermal of t' in the thermodynamic surface of the substance in question must
therefore have the same equations in the part in which v exceeds the constant v'.
Now if at any point in this surface p < 0 and t> 0 the equation of the tangent plane for
that point will be
where m denotes the temperature and - n the pressure for the point of contact, so that
m and n are both positive. Now it is evidently possible to give so large a value to
v in the equations of the isothermal that the point thus determined shall fall below the
tangent plane. Therefore, the tangent plane cuts the primitive surface, and the point
of the thermodynamic surface for which />-<0 cannot belong to the surfaces mentioned
in the last paragraph as forming a continuous sheet.
G. I. D
50 REPRESENTATION BY SURFACES OF THE
such as at the close of the processes are left in their initial con-
dition. This has been called the available energy of the body. The
initial state of the body is supposed to be such that the body can
be made to pass from it to states of dissipated energy by reversible
processes.
If the body is in a state represented by any point of the surface of
dissipated energy, of course no work can be obtained from it under
the given conditions. But even if the body is in a state of thermody-
namic equilibrium, and therefore in one represented by a point in the
thermodynamic surface, if this point is not in the surface of dissipated
energy, because the equilibrium of the body is unstable in regard to
discontinuous changes, a certain amount of energy will be available
under the conditions for the production of work. Or, if the body is
solid, even if it is uniform in state throughout, its pressure (or tension)
may have different values in different directions, and in this way it
may have a certain available energy. Or, if different parts of the
body are in different states, this will in general be a source of avail-
able energy. Lastly, we need not exclude the case in which the body
has sensible motion and its vis viva constitutes available energy. In
any case, we must find the initial volume, entropy, and energy of the
body, which will be equal to the sums of the initial volumes, entropies,
and energies of its parts. (' Energy ' is here used to include the vis
viva of sensible motions.) These values of v, r\, and e will determine
the position of a certain point which we will speak of as representing
the initial state.
Now the condition that no heat shall be allowed to pass, to ex-
ternal bodies, requires that the final entropy of the body shall not be
less than the initial, for it could only be made less by violating this
condition. The problem, therefore, may be reduced to this, — to find
the amount by which the energy of the body may be diminished
without increasing its volume or diminishing its entropy. This
quantity will be represented geometrically by the distance of the
point representing the initial state from the surface of dissipated
energy measured parallel to the axis of e.
Let us consider a different problem. A certain initial state of the
body is given as before. No work is allowed to be done upon or by
external bodies. Heat is allowed to pass to and from them only on
condition that the algebraic sum of all heat which thus passes shall
be 0. From both these conditions any bodies may be excepted, which
shall be left at the close of the processes in their initial state. More-
over, it is not allowed to increase the volume of the body. It is
required to find the greatest amount by which it is possible under
these conditions to diminish the entropy of an external system.
This will be, evidently, the amount by which the entropy of the
THERMODYNAMIC PROPERTIES OF SUBSTANCES.
51
body can be increased without changing the energy of the body
or increasing its volume, which is represented geometrically by the
distance of the point representing the initial state from the surface
of dissipated energy, measured parallel to the axis of rj. This might
be called the capacity for entropy of the body in the given state.*
* It may be worth while to call attention to the analogy and the difference between
this problem and the preceding. In the first case, the question is virtually, how great
a weight does the state of the given body enable us to raise a given distance, no other
permanent change being produced in external bodies? In the second case, the question
is virtually, what amount of heat does the state of the given body enable us to
take from an external body at a fixed temperature, and impart to another at a higher
fixed temperature? In order that the numerical values of the available energy and
of the capacity for entropy should be identical with the answers to these questions, it
would be necessary in the first case, if the weight is measured in units of force, that
the given distance, measured vertically, should be the unit of length, and in the second
case, that the difference of the reciprocals of the fixed temperatures should be unity.
If we prefer to take the freezing and boiling points as the fixed temperatures, as
TH~Tfj= 0*00098, the capacity for entropy of the body in any given condition
would be 0*00098 times the amount of heat which it would enable us to raise from the
freezing to the boiling point (i.e., to take from the body of which the temperature
remains fixed at the freezing point, and impart to another of which the temperature
remains fixed at the boiling point).
Q
The relations of these quantities to one another and to the surface of dissipated
energy are illustrated by figure 3, which represents a plane perpendicular to the axis
of v and passing through the point A, which represents the initial state of the body.
MN is the section of the surface of dissipated energy. Qe and QT; are sections of the
planes r) = 0 and e = 0, and therefore parallel to the axes of e and 77 respectively. AD and
AE are the energy and entropy of the body in its initial state, AB and AC its available
energy and its capacity for entropy respectively. It will be observed that when either
the available energy or the capacity for entropy of the body is 0, the other has the same
value. Except in this case, either quantity may be varied without affecting the other.
For, on account of the curvature of the surface of dissipated energy, it is evidently
possible to change the position of the point representing the initial state of the body so
as to vary its distance from the surface measured parallel to one axis without varying
that measured parallel to the other.
As the different sense in which the word entropy has been used by different
writers is liable to cause misunderstanding, it may not be out of place to add a
52 REPRESENTATION BY SURFACES OF THE
Thirdly. A certain initial condition of the body is given as before.
No work is allowed to be done upon or by external bodies, nor any
heat to pass to or from them ; from which conditions bodies may be
excepted, as before, in which no permanent changes are produced.
It is required to find the amount by which the volume of the body
can be diminished, using for that purpose, according to the conditions,
only the force derived from the body itself. The conditions require
that the energy of the body shall not be altered nor its entropy
diminished. Hence the quantity sought is represented by the distance
of the point representing the initial state from the surface of dissi-
pated energy, measured parallel to the axis of volume.
Fourthly. An initial condition of the body is given as before. Its
volume is not allowed to be increased. No work is allowed to be
done upon or by external bodies, nor any heat to pass to or from
them, except a certain body of given constant temperature if. From
the latter conditions may be excepted as before bodies in which no
permanent changes are produced. It is required to find the greatest
amount of heat which can be imparted to the body of constant
temperature, and also the greatest amount of heat which can be taken
from it, under the supposed conditions. If through the point of the
few words on the terminology of this subject. If Professor Clausius had defined
entropy so that its value should be determined by the equation
instead of his equation (Mechanische Warmetheorie, Abhand. ix. § 14; Pogg. Ann.
July, 1865)
where S denotes the entropy and T the temperature of a body and dQ the element of
heat imparted to it, that which is here called capacity for entropy would naturally be
called available entropy, a term the more convenient on account of its analogy with the
term available energy. Such a difference in the definition of entropy would involve no
difference in the form of the thermodynamic surface, nor in any of our geometrical
constructions, if only we suppose the direction in which entropy is measured to be
reversed. It would only make it necessary to substitute -77 for 77 in our equations,
and to make the corresponding change in the verbal enunciation of propositions.
Professor Tait has proposed to use the word entropy " in the opposite sense to that in
which Clausius has employed it" (Thermodynamics, % 48. See also § 178), which
appears to mean that he would determine its value by the first of the above equations.
He nevertheless appears subsequently to use the word to denote available energy
(§ 182, 2d theorem). Professor Maxwell uses the word entropy as synonymous with
available energy, with the erroneous statement that Clausius uses the word to denote
the part of the energy which is not available (Theory of Heat, pp. 186 and 188). The
term entropy, however, as used by Clausius does not denote a quantity of the same
kind (i.e., one which can be measured by the same unit) as energy, as is evident from
his equation, cited above, in which Q (heat) denotes a quantity measured by the unit
of energy, and as the unit in which T (temperature) is measured is arbitrary, S and Q
are evidently measured by different units. It may be added that entropy as defined
by Clausius is synonymous with the thermodynamic function as defined by Rankine.
THERMODYNAMIC PROPERTIES OF SUBSTANCES. 53
initial state a straight line be drawn in the plane perpendicular to
the axis of v, so that the tangent of the angle which it makes with
the direction of the axis of r\ shall be equal to the given temperature
if, it may easily be shown that the vertical projections of the two
segments of this line made by the point of the initial state and the
surface of dissipated energy represent the two quantities required.*
These problems may be modified so as to make them approach
more nearly the economical problems which actually present them-
selves, if we suppose the body to be surrounded by a medium of
constant pressure and temperature, and let the body and the medium
together take the place of the body in the preceding problems. The
results would be as follows :
If we suppose a plane representing the constant pressure and tem-
perature of the medium to be tangent to the surface of dissipated
energy of the body, the distance of the point representing the initial
state of the body from this plane measured parallel to the axis, of e
will represent the available energy of the body and medium, the
distance of the point to the plane measured parallel to the axis of ij
will represent the capacity for entropy of the body and medium, the
distance of the point to the plane measured parallel to the axis of v
will represent the magnitude of the greatest vacuum which can be
produced in the body or medium (all the power used being derived
from the body and medium); if a line be drawn through the point
in a plane perpendicular to the axis of v, the vertical projection of the
segment of this line made by the point and the tangent plane will
represent the greatest amount of heat which can be given to or taken
from another body at a constant temperature equal to the tangent of
the inclination of the line to the horizon. (It represents the greatest
amount which can be given to the body of constant temperature, if
this temperature is greater than that of the medium ; in the reverse
case, it represents the greatest amount which can be withdrawn from
that body.) In all these cases, the point of contact between the plane
and the surface of dissipated energy represents the final state of the
given body.
If a plane representing the pressure and temperature of the medium
be drawn through the point representing any given initial state of
the body, the part of this plane which falls within the surface of
dissipated energy will represent in respect to volume, entropy, and
energy all the states into which the body can be brought by rever-
sible processes, without producing permanent changes in external
bodies (except in the medium), and the solid figure included between
*Thus, in figure 3, if the straight line MAN be drawn so that tan NAC = *', MR
will be the greatest amount of heat which can be given to the body of constant
temperature and NS will be the greatest amount which can be taken from it.
54 REPRESENTATION BY SUEFACES, ETC.
this plane figure and the surface of dissipated energy will represent
all the states into which the body can be brought by any kind of
processes, without producing permanent changes in external bodies
(except in the medium).*
* The body under discussion has been supposed throughout this paper to be homo-
geneous in substance. But if we imagine any material system whatever, and suppose
the position of a point to be determined for every possible state of the system, by
making the co-ordinates of the point equal to the total volume, entropy, and energy
of the system, the points thus determined will evidently form a solid figure bounded
in certain directions by the surface representing the states of dissipated energy. In
these states, the temperature is necessarily uniform throughout the system ; the
pressure may vary (e.g., in the case of a very large mass like a planet), but it will always
be possible to maintain the equilibrium of the system (in a state of dissipated energy)
by a uniform normal pressure applied to its surface. This pressure and the uniform
temperature of the system will be represented by the inclination of the surface of
dissipated energy according to the rule on page 34. And in regard to such problems as
have been discussed in the last five pages, this surface will possess, relatively to the
system which it represents, properties entirely similar to those of the surface of
dissipated energy of a homogeneous body.
III.
ON THE EQUILIBEIUM OF HETEROGENEOUS
SUBSTANCES.
[Transactions of the Connecticut Academy, III. pp. 108-248, Oct. 1875-May,
1876, and pp. 343-524, May, 1877-July, 1878.]
" Die Energie der Welt 1st constant.
Die Entropie der Welt strebt einem Maximum zu."
CLAUSIUS.*
THE comprehension of the laws which govern any material system
is greatly facilitated by considering the energy and entropy of the
system in the various states of which it is capable. As the difference
of the values of the energy for any two states represents the com-
bined amount of work and heat received or yielded by the system
when it is brought from one state to the other, and the difference of
entropy is the limit of all the possible values of the integral l-X
(dQ denoting the element of the heat received from external sources,
and t the temperature of the part of the system receiving it,) the
varying values of the energy and entropy characterize in all that is
essential the effects producible by the system in passing from one
state to another. For by mechanical and thermodynamic con-
trivances, supposed theoretically perfect, any supply of work and
heat may be transformed into any other which does not differ from
it either in the amount of work and heat taken together or in the
value of the integral I ~. But it is not only in respect to the
external relations of a system that its energy and entropy are of
predominant importance. As in the case of simply mechanical sys-
tems, (such as are discussed in theoretical mechanics,) which are capable
of only one kind of action upon external systems, viz., the perform-
ance of mechanical work, the function which expresses the capability
of the system for this kind of action also plays the leading part in
the theory of equilibrium, the condition of equilibrium being that
the variation of this function shall vanish, so in a thermodynamic
system, (such as all material systems actually are,) which is capable of
* Pogg. Ami. Bd. cxxv. (1865), S. 400; or Mechanische. Wdrmetheorie, Abhand. ix.
S. 44.
56 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
two different kinds of action upon external systems, the two functions
which express the twofold capabilities of the system afford an almost
equally simple criterion of equilibrium.
Criteria of Equilibrium and Stability.
The criterion of equilibrium for a material system which is isolated
from all external influences may be expressed in either of the follow-
ing entirely equivalent forms :—
I. For the equilibrium of any isolated system it is necessary and
sufficient that in all possible variations of the state of the system
which do not alter its energy, the variation of its entropy shall either
vanish or be negative. If e denote the energy, and r\ the entropy of
the system, and we use a subscript letter after a variation to indicate
a quantity of which the value is not to be varied, the condition of
equilibrium may be written
05^0. (1)
II. For the equilibrium of any isolated system it is necessary and
sufficient that in all possible variations in the state of the system
which do not alter its entropy, the variation of its energy shall either
vanish or be positive. This condition may be written
... '•'• <&),SO. (2)
That these two theorems are equivalent will appear from the con-
sideration that it is always possible to increase both the energy and
the entropy of the system, or to decrease both together, viz., by
imparting heat to any part of the system or by taking it away. For,
if condition (1) is not satisfied, there must be some variation in the
state of the system for which
<ty>0 and (5e = 0;
therefore, by diminishing both the energy and the entropy of the
system in its varied state, we shall obtain a state for which (considered
as a variation from the original state)
<fy = 0 and <te<0;
therefore condition (2) is not satisfied. Conversely, if condition (2)
is not satisfied, there must be a variation in the state of the system
for which
<Je<0 and cty = 0;
hence tfcere must also be one for which
<$e = 0 and &/>0;
therefore condition (1) is not satisfied.
The equations which express the condition of equilibrium, as also
its statement in words, are to be interpreted in accordance with the
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 57
general usage in respect to differential equations, that is, infinitesimals
of higher orders than the first relatively to those which express the
amount of change of the system are to be neglected. But to distin-
guish the different kinds of equilibrium in respect to stability, we
must have regard to the absolute values of the variations. We will
use A as the sign of variation in those equations which are to be con-
strued strictly, i.e., in which infinitesimals of the higher orders are
not to be neglected. With this understanding, we may express the
necessary and sufficient conditions of the different kinds of equi-
librium as follows ; — for stable equilibrium
(Atf).<0, i.e., (Ae)r?>0; (3)
for neutral equilibrium there must be some variations in the state of
the system for which
(A*). = 0, i.e., (Ae),= 0; (4)
while in general
(A^)e^O, i.e., (Ae)^O; (5)
and for unstable equilibrium there must be some variations for which
(A<?)«>0, ' ..-';"• (6)
i.e., there must be some for which
(A6),<0, (7)
while in general
(&7)<^0, i.e., (<H = 0- (8)
In these criteria of equilibrium and stability, account is taken only
of possible variations. It is necessary to explain in what sense this is
to be understood. In the first place, all variations in the state of
the system which involve the transportation of any matter through
any finite distance are of course to be excluded from consideration,
although they may be capable of expression by infinitesimal varia-
tions of quantities which perfectly determine the state of the system.
For example, if the system contains two masses of the same sub-
stance, not in contact, nor connected by other masses consisting of
or containing the same substance or its components, an infinitesimal
increase of the one mass with an equal decrease of the other is not to
be considered as a possible variation in the state of the system. In
addition to such cases of essential impossibility, if heat can pass by
conduction or radiation from every part of the system to every other,
only those variations are to be rejected as impossible, which involve
changes which are prevented by passive forces or analogous resist-
ances to change. But, if the system consist of parts between which
there is supposed to be no thermal communication, it will be neces-
sary to regard as impossible any diminution of the entropy of any of
these parts, as such a change can not take place without the passage
of heat. This limitation may most conveniently be applied to the
58 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
second of the above forms of the condition of equilibrium, which will
then become / « \ > n /Qx
(0eM V, etc. = 0, (9)
rf, ty", etc., denoting the entropies of the various parts between which
there is no communication of heat. When the condition of equi-
librium is thus expressed, the limitation in respect to the conduction
of heat will need no farther consideration.-'
In order to apply to any system the criteria of equilibrium which
have been given, a knowledge is requisite of its passive forces or
resistances to change, in so far, at least, as they are capable of pre-
venting change. (Those passive forces which only retard change,
like viscosity, need not be considered.) Such properties of a system
are in general easily recognized upon the most superficial knowledge
of its nature. As examples, we may instance the passive force of
friction which prevents sliding when two surfaces of solids are
pressed together, — that which prevents the different components of
a solid, and sometimes of a fluid, from having different motions one
from another, — that resistance to change which sometimes prevents
either of two forms of the same substance (simple or compound),
which are capable of existing, from passing into the other, — that
which prevents the changes in solids which imply plasticity, (in other
words, changes of the form to which the solid tends to return,) when
the deformation does not exceed certain limits.
It is a characteristic of all these passive resistances that they pre-
vent a certain kind of motion or change, however the initial state of
the system may be modified, and to whatever external agencies of force
and heat it may be subjected, within limits, it may be, but yet within
limits which allow finite variations in the values of all the quanti-
ties which express the initial state of the system or the mechanical
or thermal influences acting on it, without producing the change in
question. The equilibrium which is due to such passive properties
is thus widely distinguished from that caused by the balance of the
active tendencies of the system, where an external influence, or a
change in the initial state, infinitesimal in amount, is sufficient to pro-
duce change either in the positive or negative direction. Hence the
ease with which these passive resistances are recognized. Only in
the case that the state of the system lies so near the limit at which
the resistances cease to be operative to prevent change, as to create a
doubt whether the case falls within or without the limit, will a more
accurate knowledge of these resistances be necessary.
To establish the validity of the criterion of equilibrium, we will
consider first the sufficiency, and afterwards the necessity, of the con-
dition as expressed in either of the two equivalent forms.
In the first place, if the system is in a state in which its entropy is
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 59
greater than in any other state of the same energy, it is evidently in
equilibrium, as any change of state must involve either a decrease of
entropy or an increase of energy, which are alike impossible for an iso-
lated system. We may add that this is a case of stable equilibrium, as
no infinitely small cause (whether relating to a variation of the initial
state or to the action of any external bodies) can produce a finite
change of state, as this would involve a finite decrease of entropy or
increase of energy.
We will next suppose that the system has the greatest entropy
consistent with its energy, and therefore the least energy consistent
with its entropy, but that there are other states of the same energy
and entropy as its actual state. In this case, it is impossible that
any motion of masses should take place; for if any of the energy
of the system should come to consist of vis viva (of sensible motions),
a state of the system identical in other respects but without the
motion would have less energy and not less entropy, which would be
contrary to the supposition. (But we cannot apply this reasoning to
the motion within any mass of its different components in different
directions, as in diffusion, when the momenta of the components
balance one another.) Nor, in the case supposed, can any conduction
of heat take place, for this involves an increase of entropy, as heat is
only conducted from bodies of higher to those of lower temperature.
It is equally impossible that any changes should be produced by the
transfer of heat by radiation. The condition which we have sup-
posed is therefore sufficient for equilibrium, so far as the motion of
masses and the transfer of heat are concerned, but to show that the
same is true in regard to the motions of diffusion and chemical or
molecular changes, when these can occur without being accompanied
or followed by the motions of masses or the transfer of heat, we must
have recourse to considerations of a more general nature. The fol-
lowing considerations seem to justify the belief that the condition is
sufficient for equilibrium in every respect.
Let us suppose, in order to test the tenability of such a hypothesis,
that a system may have the greatest entropy consistent with its
energy without being in equilibrium. In such a case, changes in the
state of the system must take place, but these will necessarily be such
that the energy and the entropy will remain unchanged and the
system will continue to satisfy the same condition, as initially, of
having the greatest entropy consistent with its energy. Let us con-
sider the change which takes place in any time so short that the
change may be regarded as uniform in nature throughout that time.
This time must be so chosen that the change does not take place in it
infinitely slowly, which is always easy, as the change which we sup-
pose to take place cannot be infinitely slow except at particular
60 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
moments. Now no change whatever in the state of the system,
which does not alter the value of the energy, and which commences
with the same, state in which the system was supposed at the com-
mencement of the short time considered, will cause an increase of
entropy. Hence, it will generally be possible by some slight variation
in the circumstances of the case to make all changes in the state
of the system like or nearly like that which is supposed actually to
occur, and not involving a change of energy, to involve a necessary
decrease of entropy, which would render any such change impossible.
This variation may be in the values of the variables which determine
the state of the system, or in the values of the constants which deter-
mine the nature of the system, or in the form of the functions which
express its laws, — only there must be nothing in the system as modi-
fied which is thermodynamically impossible. For example, we might
suppose temperature or pressure to be varied, or the composition of
the different bodies in the system, or, if no small variations which
could be actually realized would produce the required result, we
might suppose the properties themselves of the substances to undergo
variation, subject to the general laws of matter. If, then, there is
any tendency toward change in the system as first supposed, it is a
tendency which can be entirely checked by an infinitesimal variation
in the circumstances of the case. As this supposition cannot be
allowed, we must believe that a system is always in equilibrium
when it has the greatest entropy consistent with its energy, or, in
other words, when it has the least energy consistent with its entropy.
The same considerations will evidently apply to any case in which
a system is in such a state that AT; = 0 for any possible infinitesimal
variation of the state for which Ae = 0, even if the entropy is not
the greatest of which the system is capable with the same energy.
(The term possible has here the meaning previously defined, and the
character A is used, as before, to denote that the equations are to be
construed strictly, i.e., without neglect of the infinitesimals of the
higher orders.)
The only case in which the sufficiency of the condition of equit
librium which has been given remains to be proved is that in which
in our notation &/ = 0 for all possible variations not affecting the
energy, but for some of these variations A^>0, that is, when the
entropy has in some respects the characteristics of a minimum. In
this case the considerations adduced in the last paragraph will not
apply without modification, as the change of state may be infinitely
slow at first, and it is only in the initial state that the condition
&7e = 0 holds true. But the differential coefficients of all orders of
the quantities which determine the state of the system, taken with
respect of the time, must be functions of these same quantities. None
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 61
of these differential coefficients can have any value other than 0, for
the state of the system for which Srje ^ 0. For otherwise, as it would
generally be possible, as before, by some infinitely small modification
of the case, to render impossible any change like or nearly like that
which might be supposed to occur, this infinitely small modification
of the case would make a finite difference in the value of the differ-
ential coefficients which had before the finite values, or in some of
lower orders, which is contrary to that continuity which we have
reason to expect. Such considerations seem to justify us in regarding
such a state as we are discussing as one of theoretical equilibrium;
although as the equilibrium is evidently unstable, it cannot be realized.
We have still to prove that the condition enunciated is in every
case necessary for equilibrium. It is evidently so in all cases in which
the active tendencies of the system are so balanced that changes of
every kind, except those excluded in the statement of the condition of
equilibrium, can take place reversibly, (i.e., both in the positive and
the negative direction,) in states of the system differing infinitely little
from the state in question. In this case, we may omit the sign of
inequality and write as the condition of such a state of equilibrium
0, i.e., (<H = 0- (10)
But to prove that the condition previously enunciated is in every
case necessary, it must be shown that whenever an isolated system
remains without change, if there is any infinitesimal variation in its
state, not involving a finite change of position of any (even an infini-
tesimal part) of its matter, which would diminish its energy by a
quantity which is not infinitely small relatively to the variations of
the quantities which determine the state of the system, without
altering its entropy, — or, if the system has thermally isolated parts,
without altering the entropy of any such part, — this variation involves
changes in the system which are prevented by its passive forces or
analogous resistances to change. Now, as the described variation in
the state of the system diminishes its energy without altering its
entropy, it must be regarded as theoretically possible to produce that
variation by some process, perhaps a very indirect one, so as to gain
a certain amount of work (above all expended on the system). Hence
we may conclude that the active forces or tendencies of the system
favor the variation in question, and that equilibrium cannot subsist
unless the variation is prevented by passive forces.
The preceding considerations will suffice, it is believed, to establish
the validity of the criterion of equilibrium which has been given.
The criteria of stability may readily be deduced from that of equi-
librium. We will now proceed to apply these principles to systems
consisting of heterogeneous substances and deduce the special laws
62 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
which apply to different classes of phenomena. For this purpose we
shall use the second form of the criterion of equilibrium, both because
it admits more readily the introduction of the condition that there
shall be no thermal communication between the different parts of the
system, and because it is more convenient, as respects the form of
the general equations relating to equilibrium, to make the entropy
one of the independent variables which determine the state of the
system, than to make the energy one of these variables.
The Conditions of Equilibrium for Heterogeneous Masses in
Contact when Uninfluenced by Gravity, Electricity, Distortion
of the Solid Masses, or Capillary Tensions.
In order to arrive as directly as possible at the most characteristic
and essential laws of chemical equilibrium, we will first give our
attention to a case of the simplest kind. We will examine the con-
ditions of equilibrium of a mass of matter of various kinds enclosed
in a rigid and fixed envelop, which is impermeable to and unalter-
able by any of the substances enclosed, and perfectly non-conducting
to heat. We will suppose that the case is not complicated by the
action of gravity, or by any electrical influences, and that in the
solid portions of the mass the pressure is the same in every direction.
We will farther simplify the problem by supposing that the varia-
tions of the parts of the energy and entropy which depend upon the
surfaces separating heterogeneous masses are so small in comparison
with the variations of the parts of the energy and entropy which
depend upon the quantities of these masses, that the former may be
neglected by the side of the latter ; in other words, we will exclude
the considerations which belong to the theory of capillarity.
It will be observed that the supposition of a rigid and non-
conducting envelop enclosing the mass under discussion involves no
real loss of generality, for if any mass of matter is in equilibrium, it
would also be so, if the whole or any part of it were enclosed in an
envelop as supposed; therefore the conditions of equilibrium for a
mass thus enclosed are the general conditions which must always
be satisfied in case of equilibrium. As for the other suppositions
which have been made, all the circumstances and considerations
which are here excluded will afterward be made the subject of
special discussion.
Conditions relating to the Equilibrium between the initially existing
Homogeneous Parts of the given Mass.
Let us first consider the energy of any homogeneous part of the
given mass, and its variation for any possible variation in the com-
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 63
position and state of this part. (By homogeneous is meant that the
part in question is uniform throughout, not only in chemical com-
position, but also in physical state.) If we consider the amount and
kind of matter in this homogeneous mass as fixed, its energy e is a
function of its entropy rj, and its volume v, and the differentials of
these quantities are subject to the relation
de — tdri—pdv, (11)
t denoting the (absolute) temperature of the mass, and p its pressure.
For t dtj is the heat received, and p dv the work done, by the mass
during its change of state. But if we consider the matter in the
mass as variable, and write m^ m2, . . . mn for the quantities of the
various substances Slt S2, ... Sn of which the mass is composed, e will
evidently be a function of rj, v, tnlt ra2, . . . mn, and we shall have for
the complete value of the differential of €
de = tdt] —p dv + fadm^ + fJL2dm2 . . . + pndmn, (12)
fjLlt /z2, ... fJLn denoting the differential coefficients of e taken with
respect to m^ w2, . . . mH.
The substances Sl} 8* . . . Sn, of which we consider the mass com-
posed, must of course be such that the values of the differentials
doll, dm2,...dmn shall be independent, and shall express every
possible variation in the composition of the homogeneous mass con-
sidered, including those produced by the absorption of substances
different from any initially present. It may therefore be necessary
to have terms in the equation relating to component substances
which do not initially occur in the homogeneous mass considered,
provided, of course, that these substances, or their components, are
to be found in some part of the whole given mass.
If the conditions mentioned are satisfied, the choice of the sub-
stances which we are to regard as the components of the mass con-
sidered, may be determined entirely by convenience, and independently
of any theory in regard to the internal constitution of the mass. The
number of components will sometimes be greater, and sometimes
less, than the number of chemical elements present. For example,
in considering the equilibrium in a vessel containing water and free
hydrogen and oxygen, we should be obliged to recognize three com-
ponents in the gaseous part. But in considering the equilibrium of
dilute sulphuric acid with the vapor which it yields, we should have
only two components to consider in the liquid mass, sulphuric acid
(anhydrous, or of any particular degree of concentration) and (addi-
tional) water. If, however, we are considering sulphuric acid in a
state of maximum concentration in connection with substances which
might possibly afford water to the acid, it must be noticed that the
condition of the independence of the differentials will require that we
64 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
consider the acid in the state of maximum concentration as one of
the components. The quantity of this component will then be cap-
able of variation both in the positive and in the negative sense, while
the quantity of the other component can increase but cannot decrease
below the value 0.
For brevity's sake, we may call a substance Sa an actual component
of any homogeneous mass, to denote that the quantity ma of that
substance in the given mass may be either increased or diminished
(although we may have so chosen the other component substances
that ma = 0); and we may call a substance $& a possible component
to denote that it may be combined with, but cannot be subtracted
from the homogeneous mass in question. In this case, as we have
seen in the above example, we must so choose the component sub-
stances that mb = 0.
The units by which we measure the substances of which we regard
the given mass as composed may each be chosen independently. To
fix our ideas for the purpose of a general discussion, we may suppose
all substances measured by weight or mass. Yet in special cases, it
may be more convenient to adopt chemical equivalents as the units
of the component substances.
It may be observed that it is not necessary for the validity of
equation (12) that the variations of nature and state of the mass to
which the equation refers should be such as do not disturb its homo-
geneity, provided that in all parts of the mass the variations of
nature and state are infinitely small. For, if this last condition be
not violated, an equation like (12) is certainly valid for all the infin-
itesimal parts of the (initially) homogeneous mass ; i.e., if we write
De, Dq, etc., for the energy, entropy, etc., of any infinitesimal part,
dDe = t dDrj —p dDv + fa dDml + //2 dDm2 ... + /utn dDmn, (13)
whence we may derive equation (12) by integrating for the whole
initially homogeneous mass.
We will now suppose that the whole mass is divided into parts so
that each part is homogeneous, and consider such variations in the
energy of the system as are due to variations in the composition and
state of the several parts remaining (at least approximately) homoge-
neous, and together occupying the whole space within the envelop.
We will at first suppose the case to be such that the component sub-
stances are the same for each of the parts, each of the substances
$1, $2, . . . Sn being an actual component of each part. If we distinguish
the letters referring to the different parts by accents, the variation in
the energy of the system may be expressed by Se' + <$e" + etc., and the
general condition of equilibrium requires that
•" + etc. ^0 (14)
EQUILIBRIUM QF HETEROGENEOUS SUBSTANCES.
65
for all variations which do not conflict with the equations of condi-
tion. These equations must express that the entropy of the whole
given mass does not vary, nor itejyojljnig^or the total quantities oT
any of the substances $,, &,, ... Sn. We will suppose that there are
no other equations of condition. It will then be necessary for
equilibrium that
-p'W +yM/($m1/ +/z2/(Sm2/ ... +/zn'<$mn'
... +fJLn"Smn"
for any values of the variations for which
f" + etc. = 0,
^ + etc. = 0, '
'" + etc. = 0,
(15)
(16)
(17)
' -'
Smnf + Smn" + Smn'" + etc. = 0. \
For this it is evidently necessary and sufficient that
/ =3," =2,'" = etc.
(19)
(20)
(21)
Equations (19) and (20) express the conditions of thermal and
mechanical equilibrium, viz., that the temperature and the pressure
must be constant throughout the whole mass. In equations (21) we
have the conditions characteristic of chemical equilibrium. If we
call a quantity JULX) as defined by such an equation as (12), the potential
for the substance Sx in the homogeneous mass considered, these con-
ditions may be expressed as follows : —
The potential for each component substance must be constant
throughout the whole mass.
It will be remembered that we have supposed that there is no
restriction upon the freedom of motion or combination of the com-
ponent substances, and that each is an actual component of all parts
of the given mass.
The state of the whole mass will be completely determined (if we
regard as immaterial the position and form of the various homoge-
neous parts of which it is composed), when the values are determined
of the quantities of which the variations occur in (15). The number
G.I. E
66 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
of these quantities, which we may call the independent variables, is
evidently (n+2)v, v denoting the number of homogeneous parts
into which the whole mass is divided. All the quantities which
occur in (19), (20), (21), are functions of these variables, and may be
regarded as known functions, if the energy of each part is known as
a function of its entropy, volume, and the quantities of its com-
ponents. (See eq. (12).) Therefore, equations (19), (20), (21), may
be regarded as (v— 1) (n + 2) independent equations between the
independent variables. The volume of the whole mass and the total
quantities of the various substances being known afford n+1 addi-
tional equations. If we also know the total energy of the given
mass, or its total entropy, we will have as many equations as there
are independent variables.
But if any of the substances Sv S2, ... Sn are only possible com-
ponents of some parts of the given mass, the variation Sm of the
quantity of such a substance in such a part cannot have a negative
value, so that the general condition of equilibrium (15) does not
require that the potential for that substance in that part should be
equal to the potential for the same substance in the parts of which it
is an actual component, but only that it shall not be less. In this
case instead of (21) we may write
for all parts of which Sl is an actual component, and
for all parts of which 81 is a possible (but not actual) component,
['(22)
for all parts of which 82 is an actual component, and
for all parts of which 82 is a possible (but not actual) component,
etc.,
Mv M2, etc., denoting constants of which the value is only determined
by these equations.
If we now suppose that the components (actual or possible) of the
various homogeneous parts of the given mass are not the same,
the result will be of the same character as before, provided that all the
different components are independent (i.e., that no one can be made
out of the others), so that the total quantity of each component is
fixed. The general condition of equilibrium (15) and the equations
of condition (16), (17), (18) will require no change, except that, if any
of the substances 8V S2)... 8n is not a component (actual or possible) of
any part, the term fj. Sm for that substance and part will be wanting
in the former, and the Sm in the latter. This will require no change in
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 67
the form of the particular conditions of equilibrium as expressed by
(19), (20), (22); but the number of single conditions contained in (22)
is of course less than if all the component substances were components
of all the parts. Whenever, therefore, each of the different homo-
geneous parts of the given mass may be regarded as composed of some
or of all of the same set of substances, no one of which can be formed
out of the others, the condition which (with equality of temperature
and pressure) is necessary and sufficient for equilibrium between the
different parts of the given mass may be expressed as follows :—
The potential for each of tlie component substances must have a
constant value in all parts of the given mass of which that substance
is an actual component, and have a value not less than this in all
parts of which it is a possible component
The number of equations afforded by these conditions, after elimi-
nation of Mv M2, ... Mn, will be less than (n + 2)(v— 1) by the number
of terms in (15) in which the variation of the form 8m is either-
necessarily nothing or incapable of a negative value. The number of
variables to be determined is diminished by the same number, or, if
we choose, we may write an equation of the form m = 0 for each of
these terms. But when the substance is a possible component of the
part concerned, there will also be a condition (expressed by ^) to
show whether the supposition that the substance is not an actual
component is consistent with equilibrium.
We will now suppose that the substances Sv 82, ... 8n are not all
independent of each other, i.e., that some of them can be formed
out of others. We will first consider a very simple case. Let /S>3 be
composed of 8l and $2 combined in the ratio of a to b, S1 and 82
occurring as actual components in some parts of the given mass, and
8B in other parts, which do not contain 8l and $2 as separately
variable components. The general condition of equilibrium will still
have the form of (15) with certain of the terms of the form ju.8m
omitted. It may be written more briefly
^(t8r)) — ^l(p8v)-\-^(fj.l8ml)-\-^l(juL28mz} ... + Z(/zw<5mn)=0, (23)
the sign S denoting summation in regard to the different parts of
the given mass. But instead of the three equations of condition,
2 8m, =0, 2 ($?fto = 0, 2 8m.> = 0, (24)
A * £» * O * \ . /
we shall have the two,
a
i £ dm3 = U,
(25)
The other equations of condition,
= 0, etc., (26)
68 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
will remain unchanged. Now as all values of the variations which
satisfy equations (24) will also satisfy equations (25), it is evident
that all the particular conditions of equilibrium which we have
already deduced, (19), (20), (22), are necessary in this case also.
When these are satisfied, the general condition (23) reduces to
M£ 8ml + 1T22 <$ w2 + Jf82 Sms ^ 0. (27)
For, although it may be that ///, for example, is greater than Mv
yet it can only be so when the following Sm^ is incapable of a nega-
tive value. Hence, if (27) is satisfied, (23) must also be. Again, if
(23) is satisfied, (27) must also be satisfied, so long as the variation
of the quantity of every substance has the value 0 in all the parts of
which it is not an actual component. But as this limitation does not
affect the range of the possible values of 2£m1, S$m2, and E£m3,
it may be disregarded. Therefore the conditions (23) and (27) are
entirely equivalent, when (19), (20), (22) are satisfied. Now, by
means of the equations of condition (25), we may eliminate 'ZSml
and 2$w2 from (27), which becomes
- a Af X2 Sm3 - b M<£ Sm3 + (a + b) M<£ 8m3 ^ 0, (28)
i.e., as the value of 2 <5m3 may be either positive or negative,
aMl + b Mz = (a + 6) M» (29)
which is the additional condition of equilibrium which is necessary
in this case.
The relations between the component substances may be less
simple than in this case, but in any case they will only affect the
equations of condition, and these may always be found without .diffi-
culty, and will enable us to eliminate from the general condition of
equilibrium as many variations as there are equations of condition,
after which the coefficients of the remaining variations may be set
equal to zero, except the coefficients of variations which are incapable
of negative values, which coefficients must be equal to or greater
than zero. It will be easy to perform these operations in each par-
ticular case, but it may be interesting to see the form of the resultant
equations in general.
We will suppose that the various homogeneous parts are considered
as having in all n components, 8V $2, . . . Sn> and that there is no
restriction upon their freedom of motion and combination. But we
will so far limit the generality of the problem as to suppose that
each of these components is an actual component of some part of
the given mass.* If some of these components can be formed out
*When we come to seek the conditions of equilibrium relating to the formation of
masses unlike any previously existing, we shall take up de novo the whole problem
of the equilibrium of heterogeneous masses enclosed in a non-conducting envelop,
and give it a more general treatment, which will be free from this limitation.
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 69
of others, all such relations can be expressed by equations such as
a@ft + j8@6 + etc. = ic©fc + X@I + ete. (30)
where <Sa, <56, @t> etc. denote the units of the substances Sa, $b, Sk, etc.,
(that is, of certain of the substances Sv S2,... Sn,) and a, /#, K,
etc. denote numbers. These are not, it will be observed, equations
between abstract quantities, but the sign = denotes qualitative as
well as quantitative equivalence. We will suppose that there are
r independent equations of this character. The equations of con-
dition relating to the component substances may easily be derived
from these equations, but it will not be necessary to consider them
particularly. It is evident that they will be satisfied by any values
of the variations which satisfy equations (18); hence, the particular
conditions of equilibrium (19), (20), (22) must be necessary in this
case, and, if these are satisfied, the general equation of equilibrium
(15) or (23) will reduce to
M^ dm, + 3/22 8m2 . . . + Mn1 Smn > 0. (31)
This will appear from the same considerations which were used in
regard to equations (23) and (27). Now it is evidently possible to
give to 2<Sma, 2<Sm6, 2<$mfc, etc. values proportional to a, /3, — K,
etc. in equation (30), and also the same values taken negatively,
making 2 Sm = 0 in each of the other terms ; therefore
a^a + /W6 + etc. ...-/clffc-X^-etc. = 0, (32)
or, a^a + /W& + etc. = /cJlf* + X^ + eta (33)
It will be observed that this equation has the same form and coeffi-
cients as equation (30), M taking the place of @. It is evident that
there must be a similar condition of equilibrium for every one of the
r equations of which (30) is an example, which may be obtained
simply by changing © in these equations into M. When these
conditions are satisfied, (31) will be satisfied with any possible values
of 2 6mv 2 Sm2, ... 2 8mn. For no values of these quantities are
possible, except such that the equation
(2Sm1)®l + (2Sm2)®z...+(28mn)®n = (), (34
after the substitution of these values, can be derived from the r equa-
tions like (30), by the ordinary processes of the reduction of linear
equations. Therefore, on account of the correspondence between (31)
and (34), and between the r equations like (33) and the r equations
like (30), the conditions obtained by giving any possible values to
the variations in (31) may also be derived from the r equations like
(33); that is, the condition (31) is satisfied if the r equations like
(33) are satisfied. Therefore the r equations like (33) are with
(19), (20), and (22) the equivalent of the general condition (15)
or (23).
70 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
For determining the state of a given mass when in equilibrium
and having a given volume and given energy or entropy, the condi-
tion of equilibrium affords an additional equation corresponding to
each of the r independent relations between the n component sub-
stances. But the equations which express our knowledge of the
matter in the given mass will be correspondingly diminished, being
n — r in number, like the equations of condition relating to the
quantities of the component substances, which may be derived from
the former by differentiation.
Conditions relating to the possible Formation of Masses Unlike any
Previously Existing.
The variations which we have hitherto considered do not embrace
every possible infinitesimal variation in the state of the given mass,
so that the particular conditions already formed, although always
necessary for equilibrium (when there are no other equations of con-
dition than such as we have supposed), are not always sufficient.
For, besides the infinitesimal variations in the state and composition
of different parts of the given mass, infinitesimal masses may be
formed entirely different in state and composition from any initially
existing. Such parts of the whole mass in its varied state as
cannot be regarded as parts of the initially existing mass which
have been infinitesimally varied in state and composition, we will
call new parts. These will necessarily be infinitely small. As it is
more convenient to regard a vacuum as a limiting case of extreme
rarefaction than to give a special consideration to the possible « for-
mation of empty spaces within the given mass, the term new parts
will be used to include any empty spaces which may be formed,
when such have not existed initially. We will use De, Dq, Dv,
Dmv Dm2, . . . Dmn to denote the infinitesimal energy, entropy, and
volume of any one of these new parts, and the infinitesimal quantities
of its components. The component substances 8lt S2, ... Sn must
now be taken to include not only the independently variable com-
ponents (actual or possible) of all parts of the given mass as initially
existing, but also the components of all the new parts, the possible
formation of which we have to consider. The character S will be
used as before to express the infinitesimal variations of the quantities
relating to those parts which are only infinitesimally varied in state
and composition, and which for distinction we will call original parts,
including under this term the empty spaces, if such exist initially,
within the envelop bounding the system. As we may divide the
given mass into as many parts as we choose, and as not only the
initial boundaries, but also the movements of these boundaries during
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 71
any variation in the state of the system are arbitrary, we may so
define the parts which we have called original, that we may consider
them as initially homogeneous and remaining so, and as initially con-
stituting the whole system.
The most general value of the variation of the energy of the whole
system is evidently
2&+2D6, (35)
the first summation relating to all the original parts, and the second
to all the new parts. (Throughout the discussion of this problem, the
letter 8 or D following 2 will sufficiently indicate whether the sum-
mation relates to the original or to the new parts.) Therefore the
general condition of equilibrium is
S<5e+2De^O, (36)
or, if we substitute the value of Se taken from equation (12),
2I)e+2(^77)-2(^^)+S(//1^m1)+2(//25m2)...H-2(/zn^mn)^0. (37)
If any of the substances Sv S2, ... Sn can be formed out of others,
we will suppose, as before (see page 69), that such relations are
expressed by equations between the units of the different substances.
Let these be
oA + <^©2 •••+««©* = <>1
&i®i + &2®2 • • • + 6n®« = 0 1 r equations. (38)
etc.
The equations of condition will be (if there is no restriction upon the
freedom of motion and composition of the components)
0, (39)
0, (40)
and n — r equations of the form
etc.
Now, using Lagrange's " method of multipliers," t we will subtract
*In regard to the relation between the coefficients in (41) and those in (38), the
reader will easily convince himself that the coefficients of any one of equations (41)
are such as would satisfy all the equations (38) if substituted for Slt 82, ...Sn; and
that this is the only condition which these coefficients must satisfy, except that the
n-r sets of coefficients shall be independent, i.e., shall be such as to form independent
equations ; and that this relation between the coefficients of the two sets of equations is
a reciprocal one.
tOn account of the sign ^ in (37), and because some of the variations are incapable
of negative values, the successive steps in the reasoning will be developed at greater
length than would be otherwise necessary.
72 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
T(2 Srj + 2 Drf) — P(2 Sv 4- 2 Dv) from the first member of the
general condition of equilibrium (37), T and P being constants
of which the value is as yet arbitrary. We might proceed in the
same way with the remaining equations of condition, but we may
obtain the same result more simply in another way. We will first
observe that
which equation would hold identically for any possible values of the
quantities in the parentheses, if for T of the letters &v @2, . . . ^>n were
substituted their values in terms of the others as derived from equations
(38). (Although @x, <2>2, . . . @n do not represent abstract quantities,
yet the operations necessary for the reduction of linear equations
are evidently applicable to equations (38).) Therefore, equation (42)
will hold true if for @1} @2, . . . ©n we substitute n numbers which
satisfy equations (38). Let Mv M%, . . . Mn be such numbers, i.e., let
ttjifj
Mn = 0, \ T equations, (43)
etc.
then
^(2 (Smj + 2 Dm^) + M£L Sm2 + 2
+ J/n(2 Smn + 2 Dmn) = 0. (44)
This expression, in which the values of n — r of the constants Mv
Mz, . . . Mn are still arbitrary, we will also subtract from the first
member of the general condition of equilibrium (37), which ' will
then become
-Jf12Dm1...-Jlfw2Dmw^O. (45)
That is, having assigned to T, P, Mv M2, . . . Mn any values con-
sistent with (43), we may assert that it is necessary and sufficient for
equilibrium that (45) shall hold true for any variations in the state
of the system consistent with the equations of condition (39), (40),
(41). But it will always be possible, in case of equilibrium, to assign
such values to T, P, MI} M2, . . . Mn, without violating equations (43),
that (45) shall hold true for all variations in the state of the system
and in the quantities of the various substances composing it, even
though these variations are not consistent with the equations of con-
dition (39), (40), (41). For, when it is not possible to do this, it
must be possible by applying (45) to variations in the system not
necessarily restricted by the equations of condition (39), (40), (41) to
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 73
obtain conditions in regard to T, P, Mlt M2 ..Mn, some of which
will be inconsistent with others or with equations (43). These con-
ditions we will represent by
4^0, £^0, etc, (46)
A, B, etc. being linear functions of T, P, Mv M2, ... Mn. Then it will
be possible to deduce from these conditions a single condition of the
form
a4 + /3£+etc.^O, (47)
a, /8, etc. being positive constants, which cannot hold true consistently
with equations (43). But it is evident from the form of (47) that,
like any of the conditions (46), it could have been obtained directly
from (45) by applying this formula to a certain change in the system
(perhaps not restricted by the equations of condition (39), (40), (41)).
Now as (47) cannot hold true consistently with eqs. (43), it is evident,
in the first place, that it cannot contain T or P, therefore in the
change in the system just mentioned (for which (45) reduces to (47))-
2<ty + 21ty = 0, and 2&; + 2Dt; = 0,
so that the equations of condition (39) and (40) are satisfied. Again,
for the same reason, the homogeneous function of the first degree of
MI} M2, . . . Mn in (47) must be one of which the value is fixed by
eqs. (43). But the value thus fixed can only be zero, as is evident
from the form of these equations. Therefore
0 (48)
for any values of Mv M2, . . . Mn which satisfy eqs. (43), and therefore
0 (49)
for any numerical values of <SP @2, . . . @n which satisfy eqs. (38).
This equation (49) will therefore hold true, if for r of the letters
@lf @2, . . . <Sn we substitute their values in terms of the others taken
from eqs. (38), and therefore it will hold true when we use ©j,
@2» • • • @n» as before, to denote the units of the various components.
Thus understood, the equation expresses that the values of the
quantities in the parentheses are such as are consistent with the
equations of condition (41). The change in the system, therefore,
which we are considering, is not one which violates any of the
equations of condition, and as (45) does not hold true for this change,
and for all values of T, P, Mv M2, . . . Mn which are consistent with
eqs. (43), the state of the system cannot be one of equilibrium.
Therefore it is necessary, and it is evidently sufficient for equilibrium,
that it shall be possible to assign to T, P, Mlf M2, ... Mn such values,
74 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
consistent with eqs. (43), that the condition (45) shall hold true for
any change in the system irrespective of the equations of condition
(39), (40), (41).
For this it is necessary and sufficient that
t = T, p = P, (50)
filSml^MlSmlt ]UL2Sm2^ M2Sm2, ... [j.nSmn^MnSmn (51)
for each of the original parts as previously defined, and that
De-TDq+PDv-M^m^MzDmt... ~^Dmn^O, (52)
for each of the new parts as previously defined. If to these con-
ditions we add equations (43), we may treat T, P, Mv M2,...Mn
simply as unknown quantities to be eliminated.
In regard to conditions (51), it will be observed that if a substance
Sv is an actual component of the part of the given mass distinguished
by a single accent, Sm^ may be either positive or negative, and we
shall have fj.^ = M^\ but if Sl is only a possible component of that
part, (Sm/ will be incapable of a negative value, and we will have
The formulae (50), (51), and (43) express the same particular con-
ditions of equilibrium which we have before obtained by a less general
process. It remains to discuss (52). This formula must hold true
of any infinitesimal mass in the system in its varied state which
is not approximately homogeneous with any of the surrounding
masses, the expressions De, Dq, Dv, Dml3 Dm2, . . . Dmn denoting the
energy, entropy, and volume of this infinitesimal mass, and the
quantities of the substances Sv $2> • • • Sn which we regard as comppsing
it (not necessarily as independently variable components). If there
is more than one way in which this mass may be considered as
composed of these substances, we may choose whichever is most
convenient. Indeed it follows directly from the relations existing
between Mv M2, . . . and Mn that the result would be the same in
any case. Now, if we assume that the values of -De, Dr\, Dv, Dmv
Dm2, . . . Dmn are proportional to the values of e, ?/, v, mv ra2, . . . mn for
any large homogeneous mass of similar composition, and of the same
temperature and pressure, the condition is equivalent to this, that
e-Tri + Pv-M^-M^ ... -Mnmn^0 (53)
for any large homogeneous body which can be formed out of the
substances Sv S2, ... Sn.
But the validity of this last transformation cannot be admitted
without considerable limitation. It is assumed that the relation
between the energy, entropy, volume, and the quantities of the
different components of a very small mass surrounded by substances
of different composition and state is the same as if the mass in
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 75
question formed a part of a large homogeneous body. We started,
indeed, with the assumption that we might neglect the part of the
energy, etc., depending upon the surfaces separating heterogeneous
masses. Now, in many cases, and for many purposes, as, in general,
when the masses are large, such an assumption is quite legitimate,
but in the case of these masses which are formed within or among
substances of different nature or state, and which at their first
formation must be infinitely small, the same assumption is evidently
entirely inadmissible, as the surfaces must be regarded as infinitely
large in proportion to the masses. We shall see hereafter what
modifications are necessary in our formulae in order to include the
parts of the energy, etc., which are due to the surfaces, but this will
be on the assumption, which is usual in the theory of capillarity,
that the radius of curvature of the surfaces is large in proportion to
the radius of sensible molecular action, and also to the thickness of
the lamina of matter at the surface which is not (sensibly) homo-
geneous in all respects with either of the masses which it separates-.
But although the formulae thus modified will apply with sensible
accuracy to masses (occurring within masses of a different nature)
much smaller than if the terms relating to the surfaces were omitted,
yet their failure when applied to masses infinitely small in all their
dimensions is not less absolute.
Considerations like the foregoing might render doubtful the validity
even of (52) as the necessary and sufficient condition of equilibrium
in regard to the formation of masses not approximately homogeneous
with those previously existing, when the conditions of equilibrium
between the latter are satisfied, unless it is shown that in establishing
this formula there have been no quantities neglected relating to the
mutual action of the new and the original parts, which can affect the
result. It will be easy to give such a meaning to the expressions
De, Dr\, Dv, Dmv Dm2, . . . Dmn that this shall be evidently the case.
It will be observed that the quantities represented by these expressions
have not been perfectly defined. In the first place, we have no right
to assume the existence of any surface of absolute discontinuity to
divide the new parts from the original, so that the position given
to the dividing surface is to a certain extent arbitrary. Even if
the surface separating the masses were determined, the energy to
be attributed to the masses separated would be partly arbitrary,
since a part of the total energy depends upon the mutual action
of the two masses. We ought perhaps to consider the case the
same in regard to the entropy, although the entropy of a system
never depends upon the mutual relations of parts at sensible dis-
tances from one another. Now the condition (52) will be valid if
the quantities De, Dq, Dv, Dmv Dm2, . . . Dmn are so defined that
76 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
none of the assumptions which have been made, tacitly or otherwise,
relating to the formation of these new parts, shall be violated. These
assumptions are the following: — that the relation between the varia-
tions of the energy, entropy, volume, etc., of any of the original parts
is not affected by the vicinity of the new parts ; and that the energy,
entropy, volume, etc., of the system in its varied state are correctly
represented by the sums of the energies, entropies, volumes, etc., of
the various parts (original and new), so far at least as any of these
quantities are determined or affected by the formation of the new
parts. We will suppose De, Dr\, Dv, Dm1} Dm2> . . . Dmn to be so
defined that these conditions shall not be violated. This may be
done in various ways. We may suppose that the position of the
surfaces separating the new and the original parts has been fixed in
any suitable way. This will determine the space and the matter
belonging to the parts separated. If this does not determine the
division of the entropy, we may suppose this determined in any
suitable arbitrary way. Thus we may suppose the total energy in and
about any new part to be so distributed that equation (12) as applied
to the original parts shall not be violated by the formation of the
new parts. Or, it may seem more simple to suppose that the
imaginary surface which divides any new part from the original is
so placed as to include all the matter which is affected by the
vicinity of the new formation, so that the part or parts which we
regard as original may be left homogeneous in the strictest sense,
including uniform densities of energy and entropy, up to the very
bounding surface. The homogeneity of the new parts is of no con-
sequence, as we have made no assumption in that respect. It may
be doubtful whether we can consider the new parts, as thus bounded,
to be infinitely small even in their earliest stages of development. But
if they are not infinitely small, the only way in which this can affect
the validity of our formulse will be that in virtue of the equations of
condition, i.e., in virtue of the evident necessities of the case, finite
variations of the energy, entropy, volume, etc., of the original parts
will be caused, to which it might seem that equation (12) would not
apply. But if the nature and state of the mass be not varied, equa-
tion (12) will hold true of finite differences. (This appears at once,
if we integrate the equation under the above limitation.) Hence,
the equation will hold true for finite differences, provided that the
nature and state of the mass be infinitely little varied. For the dif-
ferences may be considered as made up of two parts, of which the
first are for a constant nature and state of the mass, and the second
are infinitely small. We may therefore regard the new parts to be
bounded as supposed without prejudice to the validity of any of our
results.
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 77
The condition (52) understood in either of these ways (or in
others which will suggest themselves to the reader) will have a
perfectly definite meaning, and will be valid as the necessary and
sufficient condition of equilibrium in regard to the formation of new
parts, when the conditions of equilibrium in regard to the original
parts, (50), (51), and (43), are satisfied.
In regard to the condition (53), it may be shown that with (50),
(51), and (43) it is always sufficient for equilibrium. To prove this,
it is only necessary to show that when (50), (51), and (43) are satisfied,
and (52) is not, (53) will also not be satisfied.
We will first observe that an expression of the form
-e + Tri-Pv + M]m1 + M2m2...+Mnmn (54)
denotes the work obtainable by the formation (by a reversible pro-
cess) of a body of which e, rj, v, m1, ra2, . . . mn are the energy, entropy,
volume, and the quantities of the components, within a medium
having the pressure P, the temperature T, and the potentials M^
Mz,...Mn. (The medium is supposed so large that its properties
are not sensibly altered in any part by the formation of the body.)
For e is the energy of the body formed, and the remaining terms
represent (as may be seen by applying equation (12) to the medium)
the decrease of the energy of the medium, if, after the formation of
the body, the joint entropy of the medium and the body, their joint
volumes and joint quantities of matter, were the same as the entropy,
etc., of the medium before the formation of the body. This con-
sideration may convince us that for any given finite values of v and
of T, P, Mv etc., this expression cannot be infinite when e, q, mv etc.,
are determined by any real body, whether homogeneous or not
(but of the given volume), even when T, P, Mv etc., do not represent
the values of the temperature, pressure, and potentials of any real
substance. (If the substances Sv S2, ... Sn are all actual components
of any homogeneous part of the system of which the equilibrium
is discussed, that part will afford an example of a body having the
temperature, pressure, and potentials of the medium supposed.)
Now by integrating equation (12) on the supposition that the
nature and state of the mass considered remain unchanged, we obtain
the equation
e = tri-pv-^fi1ml + fjL2m2 ... + /znmn, (55)
which will hold true of any homogeneous mass whatever. Therefore
for any one of the original parts, by (50) and (51),
e-Trj + Pv-Mlm1-M2m2...'-Mnmn = (). (56)
If the condition (52) is not satisfied in regard to all possible new
parts, let ^ be a new part occurring in an original part 0, for which
78 EQUILIBEIUM OF HETEROGENEOUS SUBSTANCES.
the condition is not satisfied. It is evident that the value of the
expression e-Tr,+Pv-Mlml-M^m,_...-Mnmn (57)
applied to a mass like 0 including some very small masses like N,
will be negative, and will decrease if the number of these masses like
N is increased, until there remains within the whole mass no portion
of any sensible size without these masses like N, which, it will be
remembered, have no sensible size. But it cannot decrease without
limit, as the value of (54) cannot become infinite. Now we need not
inquire whether the least value of (57) (for constant values of T, Py
Mv M2, . . . Mn) would be obtained by excluding entirely the mass
like 0, and filling the whole space considered with masses like N,
or whether a certain mixture would give a smaller value, — it is
certain that the least possible value of (57) per unit of volume, and
that a negative value, will be realized by a mass having a certain
homogeneity. If the new part N for which the condition (52) is not
satisfied occurs between two different original parts 0' and 0", the
argument need not be essentially varied. We may consider the
value of (57) for a body consisting of masses like 0' and 0" separated
by a lamina N. This value may be decreased by increasing the
extent of this lamina, which may be done within a given volume
by giving it a convoluted form ; and it will be evident, as before,
that the least possible value of (57) will be for a homogeneous mass,
and that the value will be negative. And such a mass will be not
merely an ideal combination, but a body capable of existing, for as the
expression (57) has for this mass in the state considered its least
possible value per unit of volume, the energy of the mass included in
a unit of volume is the least possible for the same matter with the
same entropy and volume, — hence, if confined in a non-conducting
vessel, it will be in a state of not unstable equilibrium. Therefore
when (50), (51), and (43) are satisfied, if the condition (52) is not
satisfied in regard to all possible new parts, there will be some homo-
geneous body which can be formed out of the substances 8V S2, ... Sn
which will not satisfy condition (53).
Therefore, if the initially existing masses satisfy the conditions (50),
(51), and (43), and condition (53) is satisfied by every homogeneous
body which can be formed out of the given matter, there will be
equilibrium.
On the other hand, (53) is not a necessary condition of equilibrium.
For we may easily conceive that the condition (52) shall hold true
(for any very small formations within or between any of the given
masses), while the condition (53) is not satisfied (for all large masses
formed of the given matter), and experience shows that this is very
often the case. Supersaturated solutions, superheated water, etc.,
EQUILIBKIUM OF HETEROGENEOUS SUBSTANCES. 79
are familiar examples. Such an equilibrium will, however, be practi-
cally unstable. By this is meant that, although, strictly speaking,
an infinitely small disturbance or change may not be sufficient to
destroy the equilibrium, yet a very small change in the initial state,
perhaps a circumstance which entirely escapes our powers of percep-
tion, will be sufficient to do so. The presence of a small portion of
the substance for which the condition (53) does not hold true, is
sufficient to produce this result, when this substance forms a variable
component of the original homogeneous masses. In other cases,
when, if the new substances are formed at all, different kinds must
be formed simultaneously, the initial presence of the different kinds,
and that in immediate proximity, may be necessary.
It will be observed, that from (56) and (53) we can at once obtain
(50) and (51), viz., by applying (53) to bodies differing infinitely
little from the various homogeneous parts of the given mass. There-
fore, the condition (56) (relating to the various homogeneous parts
of the given mass) and (53) (relating to any bodies which can be"
formed of the given matter) with (43) are always sufficient for equi-
librium, and always necessary for an equilibrium which shall be
practically stable. And, if we choose, we may get rid of limitation
in regard to equations (43). For, if we compare these equations
with (38), it is easy to see that it is always immaterial, in applying
the tests (56) and (53) to any body, how we consider it to be com-
posed. Hence, in applying these tests, we may consider all bodies
to be composed of the ultimate components of the given mass. Then
the terms in (56) and (53) which relate to other components than
these will vanish, and we need not regard the equations (43). Such
of the constants Mv M2, . . . Mn as relate to the ultimate components,
may be regarded, like T and P, as unknown quantities subject only
to the conditions (56) and (53).
These two conditions, which are sufficient for equilibrium and
necessary for a practically stable equilibrium, may be united in one,
viz. (if we choose the ultimate components of the given mass for the
component substances to which mv m2, . . . mn relate), that it shall be
possible to give such values to the constants T, P, Mv M2, . . . Mn in
the expression (57) that the value of the expression for each of the
homogeneous parts of the mass in question shall be as small as for
any body whatever made of the same components.
Effect of Solidity of any Part of the given Mass.
If any of the homogeneous masses of which the equilibrium is in
question are solid, it will evidently be proper to treat the proportion
of their components as invariable in the application of the criterion
80 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
of equilibrium, even in the case of compounds of variable proportions,
i.e., even when bodies can exist which are compounded in proportions
infinitesimally varied from those of the solids considered. (Those
solids which are capable of absorbing fluids form of course an
exception, so far as their fluid components are concerned.) It is true
that a solid may be increased by the formation of new solid matter
on the surface where it meets a fluid, which is not homogeneous with
the previously existing solid, but such a deposit will properly be
treated as a distinct part of the system (viz., as one of the parts
which we have called new). Yet it is worthy of notice that if a homo-
geneous solid which is a compound of variable proportions is in
contact and equilibrium with a fluid, and the actual components of
the solid (considered as of variable composition) are also actual com-
ponents of the fluid, and the condition (53) is satisfied in regard to
all bodies which can be formed out of the actual components of the
fluid (which will always be the case unless the fluid is practically
unstable), all the conditions will hold true of the solid, which would
be necessary for equilibrium if it were fluid.
This follows directly from the principles stated on the preceding
pages. For in this case the value of (57) will be zero as determined
either for the solid or for the fluid considered with reference to their
ultimate components, and will not be negative for any body whatever
which can be formed of these components ; and these conditions are
sufficient for equilibrium independently of the solidity of one of the
masses. Yet the point is perhaps of sufficient importance to demand
a more detailed consideration.
Let Sa, . . . Sg be the actual components of the solid, and Sht... Sk
its possible components (which occur as actual components in the
fluid); then, considering the proportion of the components of the
solid as variable, we shall have for this body by equation (12)
de' = t'drf —pf dvf + ^dm^. . . -f fj.g'dmg'
+ jmh'dmh'. . . + fr' dm*'. (58)
By this equation the potentials //a', ... fa' are perfectly defined. But
the differentials dma', . . . dm^, considered as independent, evidently
express variations which are not possible in the sense required in
the criterion of equilibrium. We might, however, introduce them
into the general condition of equilibrium, if we should express the
dependence between them by the proper equations of condition.
But it will be more in accordance with our method hitherto, if we
consider the solid to have only a single independently variable
component Sm of which the nature is represented by the solid itself.
We may then write
(59)
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 81
In regard to the relation of the potential px to the potentials occurring
in equation (58) it will be observed, that as we have by integration
of (58) and (59)
eWfl'-pV+^'m.'.. . + //>;, (60)
and eWfl'-pV+^'m,,'; (61)
therefore fJLx'mx' = //a'ma'- • • + /Vm</- (62)
Now, if the fluid has besides 8a,...Sg and Sh,...Sk the actual
components $„ . . . Sn, we may write for the fluid
Se" = tf' 8n" -p"8v" + yu0"<5mfl". . . + Hg"$mff"
+ Vh''6mh'\.. + vk''Smk''+fi{'8m{'... + vn''8mn'', (63)
and as by supposition
m;S>z = ma'@a...+m;@, (64)
equations (43), (50), and (51) will give in this case on elimination of
the constants T, P, etc.,
t'=r,P'=rr, (65).
and mx'fjLx' = raa>a"- . . + m////'. (66)
Equations (65) and (66) may be regarded as expressing the conditions
of equilibrium between the solid and the fluid. The last condition
may also, in virtue of (62), be expressed by the equation
ma>; ... 4- m//V = ma>a". . , + m,X". (67)
But if condition (53) holds true of all bodies which can be formed
of Sa, ... Sg, Sh,... Sk, Sh... Sn, we may write for all such bodies
€ - t"ti +p"v - fjia"ma ... - fjLg"mg - /VX
... - /// 'mu - ^"m, ... - pS'm* ^ 0. (68)
(In applying this formula to various bodies, it is to be observed that
only the values of the unaccented letters are to be determined by
the different bodies to which it is applied, the values of the accented
letters being already determined by the given fluid.) Now, by (60),
(65), and (67), the value of the first member of this condition is zero
when applied to the solid in its given state. As the condition must
hold true of a body differing infinitesimally from the solid, we shall
have
,; ...- ft," dm,'
J ... - pt"dmh' ^ 0, (69)
or, by equations (58) and (65),
(//; - /za") dma'. . . + (/V - O dm;
+(/V-^//)^V...+(//;;-yu/)dm;^0. (70)
Therefore, as these differentials are all independent,
*,' =//.„",.../;.; = //;', ti £/«»",... ft' Sft"; (71)
G.I. F
82 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
which with (65) are evidently the same conditions which we would
have obtained if we had neglected the fact of the solidity of one of
the masses.
We have supposed the solid to be homogeneous. But it is evident
that in any case the above conditions must hold for every separate
point where the solid meets the fluid. Hence, the temperature and
pressure and the potentials for all the actual components of the solid
must have a constant value in the solid at the surface where it meets
the fluid. Now, these quantities are determined by the nature and
state of the solid, and exceed in number the independent variations
of which its nature and state are capable. Hence, if we reject as
improbable the supposition that the nature or state of a body can
vary without affecting the value of any of these quantities, we may
conclude that a solid which varies (continuously) in nature or state
at its surface cannot be in equilibrium with a stable fluid which con-
tains, as independently variable components, the variable components
of the solid. (There may be, however, in equilibrium with the same
stable fluid, a, finite number of different solid bodies, composed of the
variable components of the fluid, and having their nature and state
completely determined by the fluid.)*
Effect of Additional Equations of Condition.
As the equations of condition, of which we have made use, are
such as always apply to matter enclosed in a rigid, impermeable, and
non-conducting envelop, the particular conditions of equilibrium
which we have found will always be sufficient for equilibrium. But
the number of conditions necessary for equilibrium, will be diminished,
in a case otherwise the same, as the number of equations of condition
is increased. Yet the problem of equilibrium which has been treated
will sufficiently indicate the method to be pursued in all cases and the
general nature of the results.
It will be observed that the position of the various homogeneous
parts of the given mass, which is otherwise immaterial, may deter-
mine the existence of certain equations of condition. Thus, when
different parts of the system in which a certain substance is a variable
component are entirely separated from one another by parts of which
this substance is not a component, the quantity of this substance will
be invariable for each of the parts of the system which are thus
separated, which will be easily expressed by equations of condition.
Other equations of condition may arise from the passive forces (or
resistances to change) inherent in the given masses. In the problem
*The solid has been considered as subject only to isotropic stresses. The effect of
other stresses will be considered hereafter.
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 83
which we are next to consider there are equations of condition due to
a cause of a different nature.
Effect of a Diaphragm (Equilibrium of Osmotic Forces).
If the given mass, enclosed as before, is divided into two parts, each
of which is homogeneous and fluid, by a diaphragm which is capable
of supporting an excess of pressure on either side, and is permeable to
some of the components and impermeable to others, we shall have the
equations of condition
V+*f = 0, (72)
<fo/ = 0, &/' = 0, (73)
and for the components which cannot pass the diaphragm
Sma' = 0, Sma" = 0, <$ra; = 0, <$m6" = 0, etc., (74)
and for those which can
<*™*' + Smh" = 0, SmS + Sm" = 0, etc. (75)
With these equations of condition, the general condition of equilibrium
(see (15)) will give the following particular conditions :—
*W, (76)
and for the components which can pass the diaphragm, if actual
components of both masses,
^' = /C, ti = tf, etc., ; ' (77)
but not P'=P">
nor l*a' = Pa", Hb=Hb'> etc.
Again, if the diaphragm is permeable to the components in certain
proportions only, or in proportions not entirely determined yet subject
to certain conditions, these conditions may be expressed by equations
of condition, which will be linear equations between Sm^, Sm2', etc.,
and if these be known the deduction of the particular conditions of
equilibrium will present no difficulties. We will however observe
that if the components Sv S2, etc. (being actual components on each
side) can pass the diaphragm simultaneously in the proportions a1} a2,
etc. (without other resistances than such as vanish with the velocity of
the current), values proportional to av a2, etc. are possible for Sm^,
Sm2', etc. in the general condition of equilibrium, Sm^', Sm2", etc.,
having the same values taken negatively, so that we shall have for
one particular condition of equilibrium
ai fa' + a2 fa' + etc- = ai A*i" + a2 fa" + etc- (78)
There will evidently be as many independent equations of this form
as there are independent combinations of the elements which can pass
the diaphragm.
84 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
These conditions of equilibrium do not of course depend in any
way upon the supposition that the volume of each fluid mass is kept
constant, if the diaphragm is in any case supposed immovable. In
fact, we may easily obtain the same conditions of equilibrium, if we
suppose the volumes variable. In this case, as the equilibrium must
be preserved by forces acting upon the external surfaces of the fluids,
the variation of the energy of the sources of these forces must appear
in the general condition of equilibrium, which will be
/'^0, (79)
P and P" denoting the external forces per unit of area. (Compare
(14).) From this condition we may evidently derive the same
internal conditions of equilibrium as before, and in addition the
external conditions
p' = F, p" = P". (80)
In the preceding paragraphs it is assumed that the permeability of
the diaphragm is perfect, and its impermeability absolute, i.e., that it
offers no resistance to the passage of the components of the fluids in
certain proportions, except such as vanishes with the velocity, and
that in other proportions the components cannot pass at all. How
far these conditions are satisfied in any particular case is of course to
be determined by experiment.
If the diaphragm is permeable to all the n components without
restriction, the temperature and the potentials for all the components
must be the same on both sides. Now, as one may easily convince
himself, a mass having n components is capable of only n+,1 inde-
pendent variations in nature and state. Hence, if the fluid on one
side of the diaphragm remains without change, that on the other side
cannot (in general) vary in nature or state. Yet the pressure will
not necessarily be the same on both sides. For, although the pressure
is a function of the temperature and the n potentials, it may be
a many-valued function (or any one of several functions) of these
variables. But when the pressures are different on the two sides,
the fluid which has the less pressure will be practically unstable, in
the sense in which the term has been used on page 79. For
j'-tY+p'V'-tiW-ti'«h"-.. -/CXT=o, (81)
as appears from equation (12) if integrated on the supposition that
the nature and state of the mass remain unchanged. Therefore, if
p'< p" while tf = F, Ae/ =/*/', etc.,
e" - tfif' +p'v" - /*>/' - /z2'm2". . . - /z>n" < 0. (82)
This relation indicates the instability of the fluid to which the single
accents refer. (See page 79.)
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 85
But independently of any assumption in regard to the permeability
of the diaphragm, the following relation will hold true in any case in
which each of the two fluid masses may be regarded as uniform
throughout in nature and state. Let the character D be used with
the variables which express the nature, state, and quantity of the
fluids to denote the increments of the values of these quantities
actually occurring in a time either finite or infinitesimal. Then, as
the heat received by the two masses cannot exceed t'nfi' + tf'DTj", and
as the increase of their energy is equal to the difference of the heat
they receive and the work they do,
DC + De" < f Dfl' + tf Dq" -p DV -p"Dv", (83)
i.e., by (12),
/II'DWII/+/II"DWI" + //2'Dm2'+ju2"Dm2/'+etc. ^ 0, (84)
or
O. (85)
It is evident that the sign = holds true only in the limiting case in
which no motion takes place.
Definition and Properties of Fundamental Equations.
The solution of the problems of equilibrium which we have been
considering has been made to depend upon the equations which
express the relations between the energy, entropy, volume, and the
quantities of the various components, for homogeneous combinations
of the substances which are found in the given mass. The nature of
such equations must be determined by experiment. As, however, it
is only differences of energy and of entropy that can be measured, or
indeed, that have a physical meaning, the values of these quantities
are so far arbitrary, that we may choose independently for each
simple substance the state in which its energy and its entropy are
both zero. The values of the energy and the entropy of any com-
pound body in any particular state will then be fixed. Its energy
will be the sum of the work and heat expended in bringing its
components from the states in which their energies and their entropies
are zero into combination and to the state in question; and its
entropy is the value of the integral l~ for any reversible process
by which that change is effected (dQ denoting an element of the
heat communicated to the matter thus treated, and t the temperature
of the matter receiving it). In the determination both of the energy
and of the entropy, it ia understood that at the close of the process,
all bodies which have been used, other than those to which the deter-
minations relate, have been restored to their original state, with the
86 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
exception of the sources of the work and heat expended, which must
be used only as such sources.
We know, however, a priori, that if the quantity of any homo-
geneous mass containing n independently variable components varies
and not its nature or state, the quantities e, r\, v, m^ m2, . . . wn will
all vary in the same proportion ; therefore it is sufficient if we learn
from experiment the relation between all but any one of these
quantities for a given constant value of that one. Or, we may
consider that we have to learn from experiment the relation sub-
sisting between the n+2 ratios of the 7i+3 quantities e, r\, v, mv m2,
. . m,.. To fix our ideas we may take for these ratios -> -> — -> — ->
V V V V
etc., that is, the separate densities of the components, and the ratios
G Tl
1 and -5 which may be called the densities of energy and entropy.
But when there is but one component, it may be more convenient to
c Yt 1)
choose — > — > — as the three variables. In any case, it is only a func-
m m m
tion of Ti + 1 independent variables, of which the form is to be
determined by experiment.
Now if e is a known function of ?/, v, mv m2, . . . mn, as by
equation (12)
de = tdrj—pdv + imldm1 +fjL2dm2 . . . -f jmndmn, (86)
£> P> /*!> /*2> • • • Vn are functions of the same variables, which may
be derived from the original function by differentiation, and may
therefore be considered as known functions. This will make n + 3
independent known relations between the 271 + 5 variables, e, ?/, v,
mp m2, . . . mn, t, p, JULI} yu2, . . . fJLn. These are all that exist, for
of these variables, 7i + 2 are evidently independent. Now upon
these relations depend a very large class of the properties of the
compound considered, — we may say in general, all its thermal,
mechanical, and chemical properties, so far as active tendencies are
concerned, in cases in which the form of the mass does not require
consideration. A single equation from which all these relations may
be deduced we will call a fundamental equation for the substance in
question. We shall hereafter consider a more general form of the
fundamental equation for solids, in which the pressure at any point
is not supposed to be the same in all directions. But for masses
subject only to isotropic stresses an equation between e, 77, v, mv
ra2, . . . mn is a fundamental equation. There are other equations
which possess this same property.*
*M. Massieu (Comptes Rendm, T. Ixix, 1869, p. 858 and p. 1057) has shown how all
the properties of a fluid "which are considered in thermodynamics" maj' be deduced
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 87
Let >/. = e-ty, (87)
then by differentiation and comparision with (86) we obtain
d\l? = — rjdt—pdv+/uL1dml + fjL2dm2...+fjLndmn. (88)
If, then, \[s is known as a function of t, v, mly m2, . . . m^ we can
find rj, p, fiv fa, . . . /j.n in terms of the same variables. If we then
substitute for \]s in our original equation its value taken from eq. (87),
we shall have again n+3 independent relations between the same
271 + 5 variables as before.
Let x = €+pv, (89)
then by (86),
d\ = tdq + v dp + fjL1dml + //2dra2 . . . + fin dmn. (90)
If, then, x b6 known as a function of i\, p, mlt ra2, . . . ran, we can find
t, v, fJLv /z2, ... fjin in terms of the same variables. By eliminating %t
we may obtain again n-f 3 independent relations between the same
'2n + 5 variables as at first
Let f=e-ty+2>v, (91)
then, by (86),
^f = - 1 dt + v dp + fji^dm^ 4- /*2dm2 . . . + t*nd>mn. (92)
If, then, f is known as a function of t, p, mx, ra2, . . . mn, we can
find ij, v, fj.v /ULZ, ... fjin in terms of the same variables. By eliminating
f , we may obtain again n -f 3 independent relations between the same
2u + 5 variables as at first.
If we integrate (86), supposing the quantity of the compound
substance considered to vary from zero to any finite value, its nature
and state remaining unchanged, we obtain
e = tn -pv + fjilm1 + yu2?n2 ... 4- pnmnt (93)
and by (87), (89), (91)
nn, (95)
nn. (96)
The last three equations may also be obtained directly by integrating
(88), (90), and (92).
from a single function, which he calls a characteristic function of the fluid considered.
In the papers cited, he introduces two different functions of this kind, viz., a function
of the temperature and volume, which he denotes by ^, the value of which in our
notation would be - or — -^; and a function of the temperature and pressure,
' t
which he denotes by ^', the value of which in our notation would be — — — or — -.«
t t
In both cases he considers a constant quantity (one kilogram) of the fluid, which is
regarded as invariable in composition.
88 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
If we differentiate (93) in the most general manner, and compare
the result with (86), we obtain
=Q, (97)
J Jj. , 1 7 , 9 7 , « 7
or dp = dt + -£d^+-^dn2...+-^diJ.n. (98)
Hence, there is a relation between the n + 2 quantities £, j9, /£j, //2,
. . . fjLn, which, if known, will enable us to find in terms of these
quantities all the ratios of the n + 2 quantities rj, v, m1? m2, ...mn.
With (93), this will make 7i+3 independent relations between the
same 2n + 5 variables as at first.
Any equation, therefore, between the quantities
e, q, v, mp m2, ...mw, (99)
or \[,, t, v, mv ra2, ...mw, (100)
or x, rj, p, mv m»...mn, (101)
or £ t, p, mv m2,...mn, (102)
or t, p, /ZP //2, ... pn, (103)
is a fundamental equation, and any such is entirely equivalent to any
other.* For any homogeneous mass whatever, considered (in general)
as variable in composition, in quantity, and in thermodynamic state,
and having n independently variable components, to which the sub-
script numerals refer (but not excluding the case in which n = 1 and
the composition of the body is invariable), there is a relation between
the quantities enumerated in any one of the above sets, from which, if
known, with the aid only of general principles and relations, we may
deduce all the relations subsisting for such a mass between the
quantities e, ^, x, £ t], v, mv m2, ... mn, t, p, //1? //2, ... fj.n. It will be
observed that, besides the equations which define i/r, ^, and £ there is
one finite equation, (93), which subsists between these quantities
independently of the form of the fundamental equation.
*The distinction between equations which are, and which are not, fundamental, in
the sense in which the word is here used, may be illustrated by comparing an equation
between e, i), vt m^, wi2, ... mn>
with one between e, t, y, mlt mz, . . . mn.
AB,by(86), *=(;£)
\G"7/tmi
the second equation may evidently be derived from the first. '" But the first equation
cannot be derived from the second ; for an equation between
is equivalent to one between \:r} > €> v» mi> '"hi ••• mn>
which is evidently not sufficient to determine the value of ?? in terms of the other
variables.
EQUILIBKIUM OF HETEROGENEOUS SUBSTANCES. 89
Other sets of quantities might of course be added which possess
the same property. The sets (100), (101), (102) are mentioned on
account of the important properties of the quanties \[s, ^, f, and
because the equations (88), (90), (92), like (86), afford convenient
definitions of the potentials, viz.,
(104)
r» P, «* ^dm^t, p, -,n
etc., where the subscript letters denote the quantities which remain
constant in the differentiation, m being written for brevity for all the
letters mv m2, . . . mn except the one occurring in the denominator.
It will be observed that the quantities in (103) are all independent
of the quantity of the mass considered, and are those which must, in
general, have the same value in contiguous masses in equilibrium.
On the quantities \[s, x> £
The quantity ^ has been defined for any homogeneous mass by the
equation
\l^ — € — tij. (105)
We may extend this definition to any material system whatever
which has a uniform temperature throughout.
If we compare two states of the system of the same temperature,
we have
V/ - V" = e- e" - t(n' - if). (106)
If we suppose the system brought from the first to the second of
these states without change of temperature and by a reversible
process in which W is the work done and Q the heat received by
the system, then
e'-e"=TP-Q, (107)
and W-*')=Q- (108)
Hence ^/ - \f/f = W ; (109)
and for an infinitely small reversible change in the state of the
system, in which the temperature remains constant, we may write
-d\/s = dW. (110)
Therefore, — ^ is the force function of the system for constant
temperature, just as — e is the force function for constant entropy.
That is, if we consider \fr as a function of the temperature and the
variables which express the distribution of the matter in space, for
every different value of the temperature — i/r is the different force
function required by the system if maintained at that special
temperature.
90 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
From this we may conclude that when a system has a uniform
temperature throughout, the additional conditions which are necessary
and sufficient for equilibrium may be expressed by
(W,so.» (in)
When it is not possible to bring the system from one to the other
of the states to which \f/ and \/r" relate by a reversible process
without altering the temperature, it will be observed that it is not
necessary for the validity of (107)-(109) that the temperature of the
system should remain constant during the reversible process to which
W and Q relate, provided that the only source of heat or cold used
has the same temperature as the system in its initial or final state.
Any external bodies may be used in the process in any way not
affecting the condition of reversibility, if restored to their original
condition at the close of the process ; nor does the limitation in regard
to the use of heat apply to such heat as may be restored to the
source from which it has been taken.
It may be interesting to show directly the equivalence of the
conditions (111) and (2) when applied to a system of which the
temperature in the given state is uniform throughout.
If there are any variations in the state of such a system which do
not satisfy (2), then for these variations
&?<0 and &/ = 0.
If the temperature of the system in its varied state is not uniform,
we may evidently increase its entropy without altering its energy
by supposing heat to pass from the warmer to the cooler parts. And
the state having the greatest entropy for the energy €-\-Se will
necessarily be a state of uniform temperature. For this state
(regarded as a variation from the original state)
Se<0 and cty>0.
Hence, as we may diminish both the energy and the entropy by
* This general condition of equilibrium might be used instead of (2) in such problems
of equilibrium as we have considered and others which we shall consider hereafter
with evident advantage in respect to the brevity of the formulae, as the limitation
expressed by the subscript t in (111) applies to every part of the system taken
separately, and diminishes by one the number of independent variations in the state
of these parts which we have to consider. The more cumbersome course adopted in
this paper has been chosen, among other reasons, for the sake of deducing all the
particular conditions of equilibrium from one general condition, and of having the
quantities mentioned in this general condition such as are most generally used and
most simply defined ; and because in the longer formulae as given, the reader will
easily see in each case the form which they would take if we should adopt (111) as
the general condition of equilibrium, which would be in effect to take the thermal
condition of equilibrium for granted, and to seek only the remaining conditions. For
example, in the problem treated on pages 63 ff., we would obtain from (111) by (88)
a condition precisely like (15), except that the terms td-rj', tdrj", etc., would be wanting.
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 91
cooling the system, there must be a state of uniform temperature
for which (regarded as a variation of the original state)
&?<0 and cty = 0.
From this we may conclude that for systems of initially uniform
temperature condition (2) will not be altered if we limit the variations
to such as do not disturb the uniformity of temperature.
Confining our attention, then, to states of uniform temperature, we
have by differentiation of (105)
Se-tSr] = S\ls + nSt. (112)
Now there are evidently changes in the system (produced by heating
or cooling) for which
Se-tSti = Q and therefore ^ + 7/^ = 0, (113)
neither STJ nor St having the value zero. This consideration is
sufficient to show that the condition (2) is equivalent to
<te-£(ty^0, (114)
and that the condition (111) is equivalent to
W+qSt^O, (115)
and by (112) the two last conditions are equivalent.
In such cases as we have considered on pages 62-82, in which
the form and position of the masses of which the system is composed
are immaterial, uniformity of temperature and pressure are always
necessary for equilibrium, and the remaining conditions, when these
are satisfied, may be conveniently expressed by means of the
function f, which has been defined for a homogeneous mass on
page 87, and which we will here define for any mass of uniform
temperature and pressure by the same equation
£=e-tt]+pv. (116)
For such a mass, the condition of (internal) equilibrium is
<«#,., ^0. (117)
That this condition is equivalent to (2) will easily appear from con-
siderations like those used in respect to (111).
Hence, it is necessary for the equilibrium of two contiguous masses
identical in composition that the values of f as determined for equal
quantities of the two masses should be equal. Or, when one of three
contiguous masses can be formed out of the other two, it is necessary
for equilibrium that the value of f for any quantity of the first mass
should be equal to the sum of the values of f for such quantities of
the second and third masses as together contain the same matter.
Thus, for the equilibrium of a solution composed of a parts of water
92 EQUILIBEIUM OF HETEROGENEOUS SUBSTANCES.
and b parts of a salt which is in contact with vapor of water and
crystals of the salt, it is necessary that the value of f for the quantity
a+b of the solution should be equal to the sum of the values of f for
the quantities a of the vapor and 6 of the salt. Similar propositions
will hold true in more complicated cases. The reader will easily
deduce these conditions from the particular conditions of equilibrium
given on page 74.
In like manner we may extend the definition of x t° any mass or
combination of masses in which the pressure is everywhere the same,
using e for the energy and v for the volume of the whole and setting
as before
(118)
If we denote by Q the heat received by the combined masses from
external sources in any process in which the pressure is not varied,
and distinguish the initial and final states of the system by accents
we have
'-'O = Q. (H9)
This function may therefore be called the heat function for constant
pressure (just as the energy might be called the heat function for
constant volume), the diminution of the function representing in all
cases in which the pressure is not varied the heat given out by the
system. In all cases of chemical action in which no heat is allowed
to escape the value of x remains unchanged.
Potentials.
In the definition of the potentials yup /x2, etc., the energy of a
homogeneous mass was considered as a function of its entropy, its
volume, and the quantities of the various substances composing it.
Then the potential for one of these substances was defined as the
differential coefficient of the energy taken with respect to the variable
expressing the quantity of that substance. Now, as the manner in
which we consider the given mass as composed of various substances
is in some degree arbitrary, so that the energy may be considered as
a function of various different sets of variables expressing quantities
of component substances, it might seem that the above definition does
not fix the value of the potential of any substance in the given mass,
until we have fixed the manner in which the mass is to be considered
as composed. For example, if we have a solution obtained by dis-
solving in water a certain salt containing water of crystallization,
we may consider the liquid as composed of ms weight-units of the
hydrate and mw of water, or as composed of ma of the anhydrous
salt and mw of water. It will be observed that the values of ms and
EQUILIBKIUM OF HETEROGENEOUS SUBSTANCES. 93
m, are not the same, nor those of mw and raw, and hence it might
seem that the potential for water in the given liquid considered as
composed of the hydrate and water, viz.,
would be different from the potential for water in the same liquid
considered as composed of anhydrous salt and water, viz.,
( —^
\dmjn v, m, '
The value of the two expressions is, however, the same, for, although
mw is not equal to m^, we may of course suppose dm w to be equal to
dmw, and then the numerators in the two fractions will also be equal,
as they each denote the increase of energy of the liquid, when the
quantity dmw or dmw of water is added without altering the entropy
and volume of the liquid. Precisely the same considerations will
apply to any other case.
In fact, we may give a definition of a potential which shall not pre-
suppose any choice of a particular set of substances as the components
of the homogeneous mass considered.
Definition. — If to any homogeneous mass we suppose an infini-
tesimal quantity of any substance to be added, the mass remaining
homogeneous and its entropy and volume remaining unchanged, the
increase of the energy of the mass divided by the quantity of the
substance added is the potential for that substance in the mass con-
sidered. (For the purposes of this definition, any chemical element or
combination of elements in given proportions may be considered a
substance, whether capable or not of existing by itself as a homo-
geneous body.)
In the above definition we may evidently substitute for entropy,
volume, and energy, respectively, either temperature, volume, and
the function \js; or entropy, pressure, and the function ^5 or tem-
perature, pressure, and the function £ (Compare equation (104).)
In the same homogeneous mass, therefore, we may distinguish the
potentials for an indefinite number of substances, each of which has a
perfectly determined value.
Between the potentials for different substances in the same homo-
geneous mass the same equations will subsist as between the units
of these substances. That is, if the substances, Sa, Sb, etc., Sk, St, etc.,
are components of any given homogeneous mass, and are such that
a®a-h|8 @&+etc. = /c@ +X ©j+etc., (120)
<Sa, ©b, etc., ©fc, @i, etc., denoting the units of the several substances,
and a, /3, etc., /c, X, etc., denoting numbers, then if //0, fjib> etc., [JLk, fa,
94 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
etc., denote the potentials for these substances in the homogeneous
mass,
+ etc. (121)
To show this, we will suppose the mass considered to be very large.
Then, the first member of (121) denotes the increase of the energy of
the mass produced by the addition of the matter represented by the
first member of (120), and the second member of (121) denotes the
increase of energy of the same mass produced by the addition of
the matter represented by the second member of (120), the entropy
and volume of the mass remaining in each case unchanged. Therefore,
as the two members of (120) represent the same matter in kind and
quantity, the two members of (121) must be equal.
But it must be understood that equation (120) is intended to
denote equivalence of the substances represented in the mass con-
sidered, and not merely chemical identity ; in other words, it is
supposed that there are no passive resistances to change in the mass
considered which prevent the substances represented by one member
of (120) from passing into those represented by the other. For
example, in respect to a mixture of vapor of water and free hydrogen
and oxygen (at ordinary temperatures), we may not write
but water is to be treated as an independent substance, and no
necessary relation will subsist between the potential for water and
the potentials for hydrogen and oxygen.
The reader will observe that the relations expressed by equations
(43) and (51) (which are essentially relations between the potentials
for actual components in different parts of a mass in a state of
equilibrium) are simply those which by (121) would necessarily
subsist between the same potentials in any homogeneous mass con-
taining as variable components all the substances to which the
potentials relate.
In the case of a body of invariable composition, the potential for
the single component is equal to the value of f for one unit of the
body, as appears from the equation
£=/xm, : . (122)
to which (96) reduces in this case. Therefore, when 7i = l, the funda-
mental equation between the quantities in the set (102) (see page 88)
and that between the quantities in (103) may be derived either from
the other by simple substitution. But, with this single exception, an
equation between the quantities in one of the sets (99)-(103) cannot
be derived from the equation between the quantities in another of
these sets without differentiation.
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 95
Also in the case of a body of variable composition, when all the
quantities of the components except one vanish, the potential for
that one will be equal to the value of f for one unit of the body.
We may make this occur for any given composition of the body by
choosing as one of the components the matter constituting the body
itself, so that the value of f for one unit of a body may always be
considered as a potential. Hence the relations between the values
of f for contiguous masses given on page 91 may be regarded as
relations between potentials.
The two following propositions afford definitions of a potential
which may sometimes be convenient.
The potential for any substance in any homogeneous mass is equal
to the amount of mechanical work required to bring a unit of the
substance by a reversible process from the state in which its energy
and entropy are both zero into combination with the homogeneous
mass, which at the close of the process must have its original volume,
and which is supposed so large as not to be sensibly altered in any
part. All other bodies used in the process must by its close be
restored to their original state, except those used to supply the
work, which must be used only as the source of the work. For, in
a reversible process, when the entropies of other bodies are not
altered, the entropy of the substance and mass taken together will
not be altered. But the original entropy of the substance is zero;
therefore the entropy of the mass is not altered by the addition of
the substance. Again, the work expended will be equal to the
increment of the energy of the mass and substance taken together,
and therefore equal, as the original energy of the substance is zero,
to the increment of energy of the mass due to the addition of the
substance, which by the definition on page 93 is equal to the potential
in question.
The potential for any substance in any homogeneous mass is equal
to the work required to bring a unit of the substance by a reversible
process from a state in which \[s = 0 and the temperature is the same
as that of the given mass into combination with this mass, which at
the close of the process must have the same volume and temperature
as at first, and which is supposed so large as not to be sensibly
altered in any part. A source of heat or cold of the temperature
of the given mass is allowed, with this exception other bodies are
to be used only on the same conditions as before. This may be
shown by applying equation (109) to the mass and substance taken
together.
The last proposition enables us to see very easily how the value
of the potential is affected by the arbitrary constants involved in
the definition of the energy and the entropy of each elementary
96 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
substance. For we may imagine the substance brought from the state
in which \{s = 0 and the temperature is the same as that of the given
mass, first to any specified state of the same temperature, and then
into combination with the given mass. In the first part of the
process the work expended is evidently represented by the value of
\jr for the unit of the substance in the state specified. Let this be
denoted by •*}/, and let JUL denote the potential in question, and W the
work expended in bringing a unit of the substance from the specified
state into combination with the given mass as aforesaid ; then
fj. = ^'+W. (123)
Now as the state of the substance for which e = 0 and j/ = 0 is
arbitrary, we may simultaneously increase the energies of the unit
of the substance in all possible states by any constant (7, and the
entropies of the substance in all possible states by any constant K.
The value of \]s, or e — trj, for any state would then be increased by
C—tK, t denoting the temperature of the state. Applying this to
\fs' in (123) and observing that the last term in this equation is
independent of the values of these constants, we see that the potential
would be increased by the same quantity C—tK, t being the tem-
perature of the mass in which the potential is to be determined.
On Coexistent Phases of Matter.
In considering the different homogeneous bodies which can be
formed out of any set of component substances, it will be convenient
to have a term which shall refer solely to the composition and ther-
modynamic state of any such body without regard to its quantity or
form. We may call such bodies as differ in composition or state
different phases of the matter considered, regarding all bodies which
differ only in quantity and form as different examples of the same
phase. Phases which can exist together, the dividing surfaces being
plane, in an equilibrium which does not depend upon passive resist-
ances to change, we shall call coexistent.
If a homogeneous body has n independently variable components,
the phase of the body is evidently capable of n+ 1 independent
variations. A system of r coexistent phases, each of which has the
same n independently variable components is capable of n + 2 — r
variations of phase. For the temperature, the pressure, and the
potentials for the actual components have the same values in the
different phases, and the variations of these quantities are by (97)
subject to as many conditions as there are different phases. There-
fore, the number of independent variations in the values of these
quantities, i.e., the number of independent variations of phase of the
system, will be ?i-f 2— r.
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 97
Or, when the r bodies considered have not the same independently
variable components, if we still denote by n the number of inde-
pendently variable components of the r bodies taken as a whole, the
number of independent variations of phase of which the system is
capable will still be n + 2 — r. In this case, it will be necessary to
consider the potentials for more than n component substances. Let
the number of these potentials be n + h. We shall have by (97), as
before, r relations between the variations of the temperature, of the
pressure, and of these n+h potentials, and we shall also have by (43)
and (51) h relations between these potentials, of the same form as the
relations which subsist between the units of the different component
substances.
Hence, if r = n+2, no variation in the phases (remaining coex-
istent) is possible. It does not seem probable that r can ever exceed
n + 2. An example of n = 1 and r = 3 is seen in the coexistent solid,
liquid, and gaseous forms of any substance of invariable composition.
It seems not improbable that in the case of sulphur and some other
simple substances there is more than one triad of coexistent phases;
but it is entirely improbable that there are four coexistent phases of
any simple substance. An example of n = 2 and r = 4 is seen in a
solution of a salt in water in contact with vapor of water and two
different kinds of crystals of the salt.
Concerning n + l Coexistent Phases.
We will now seek the differential equation which expresses the
relation between the variations of the temperature and the pressure in
a system of n + 1 coexistent phases (n denoting, as before, the number
of independently variable components in the system taken as a whole).
In this case we have n + l equations of the general form of (97)
(one for each of the coexistent phases), in which we may distinguish
the quantities q, v, rap m2, etc., relating to the different phases by
accents. But t and p will each have the same value throughout, and
the same is true of yu1? jn2, etc., so far as each of these occurs in the
different equations. If the total number of these potentials is n+h,
there will be h independent relations between them, corresponding to
the h independent relations between the units of the component
substances to which the potentials relate, by means of which we
may eliminate the variations of h of the potentials from the equations
of the form of (97) in which they occur.
Let one of these equations be
v'dp = r)'dt + ma'djULa+mb'd[jLb + etc., (124)
and by the proposed elimination let it become
dpn> (125)
G.I. G
98
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
It will be observed that yua, for example, in (124) denotes the potential
in the mass considered for a substance Sa which may or may not
be identical with any of the substances 8V $2, etc., to which the
potentials in (125) relate. Now as the equations between the
potentials by means of which the elimination is performed are similar
to those which subsist between the units of the corresponding sub-
stances (compare equations (38), (43), and (51)), if we denote these
units by @a, <S&, etc., &v @2, etc., we must also have
ma/@a+m6'@6+etc. = ^1/@1 + ^2/(S2 ... +4 „'<§„. (126)
But the first member of this equation denotes (in kind and quantity)
the matter in the body to which equations (124) and (125) relate.
As the same must be true of the second member, we may regard this
same body as composed of the quantity A^ of the substance 8V with
the quantity A^ of the substance $2, etc. We will therefore, in
accordance with our general usage, write m/, m2', etc., for A^t A^,
etc., in (125), which will then become
v'dp = ri'dt+ml'dfj.l + m2'd]UL2... +mn'djj.n. (127)
But we must remember that the components to which the m/, m2',
etc., of this equation relate are not necessarily independently variable,
as are the components to which the similar expressions in (97) and
(124) relate. The rest of the n + l equations may be reduced to a
similar form, viz.,
v"dp = rj"dt+ml"d/uLl+m2"diuL2 ... +mn"dfjLn, (128)
etc.
By elimination of dp^ djj.2, ... dfjLn from these equations we obtain
...m^
, //
7) W 1
V llt-t li
11" m " w " vn '
(/ //I/-! I'vn . . . ilvfl
v'" >m '" m '" m '
(/ //(/i //f/9 ... 1'V'H
dp
...m
n
'
ri m m2...mw
if" m/" m9'"...mn'"
dt.
(129)
In this equation we may make i>', i>", etc., equal to unity. Then
m/, m2', w,/', etc., will denote the separate densities of the components
in the different phases, and rf, rff, etc., the densities of entropy.
When n=l,
(mV - mV)dp = (m'V - mV')rf«, (130)
or, if we make mx = 1 and m"= 1, we have the usual formula
dp_r\-rj' _Q nqn
— 7T ~^ — 7 77 ^~ j~7 — 77 7T i \ /
in which Q denotes the heat absorbed by a unit of the substance in
passing from one state to the other without change of temperature or
pressure.
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
99
Concerning Cases in which the Number of Coexistent Phases is
less than
When n > 1, if the quantities of all the components S1,S2,...Sn
are proportional in two coexistent phases, the two equations of the
form of (127) and (128) relating to these phases will be sufficient
for the elimination of the variations of all the potentials. In fact,
the condition of the coexistence of the two phases together with the
condition of the equality of the n — 1 ratios of m/, m2', . . . mn' with
the n — 1 ratios of m/', ra2", . . . mn" is sufficient to determine p as a
function of t if the fundamental equation is known for each of the
phases. The differential equation in this case may be expressed in
the form of (130), m' and w" denoting either the quantities of any
one of the components or the total quantities of matter in the bodies
to which they relate. Equation (131) will also hold true in this case
if the total quantity of matter in each of the bodies is unity. But
this case differs from the preceding in that the matter which absorbs
the heat Q in passing from one state to another, and to which the
other letters in the formula relate, although the same in quantity,
is not in general the same in kind at different temperatures and
pressures. Yet the case will often occur that one of the phases is
essentially invariable in composition, especially when it is a crystalline
body, and in this case the matter to which the letters in (131) relate
will not vary with the temperature and pressure.
When 7i = 2, two coexistent phases are capable, when the tem-
perature is constant, of a single variation in phase. But as (130)
will hold true in this case when m1':wia'::ml":m|", it follows that
for constant temperature the pressure is in general a maximum or
a minimum when the composition of the two phases is identical.
In like manner, the temperature of the two coexistent phases is in
general a maximum or a minimum, for constant pressure, when the
composition of the two phases is identical. Hence, the series of
simultaneous values of t and p for which the composition of two
coexistent phases is identical separates those simultaneous values of
t and p for which no coexistent phases are possible from those for
which there are two pair of coexistent phases. This may be applied
to a liquid having two independently variable components in con-
nection with the vapor which it yields, or in connection with any
solid which may be formed in it.
When n = 3, we have for three coexistent phases three equations
of the form of (127), from which we may obtain the following,
v
m
v m m2
v'" m/" m2'
dp =
r[ m/ m/
n" <' <'
if" m/" m2'"
dt +
rax
ra^' 77i,
m/" m
13
//
//
2 m3
/// ///
O lti/f>
dp* (132)
100 EQUILIBKIUM OF HETEROGENEOUS SUBSTANCES.
Now the value of the last of these determinants will be zero, when
the composition of one of the three phases is such as can be produced
by combining the other two. Hence, the pressure of three coexistent
phases will in general be a maximum or minimum for constant tem-
perature, and the temperature a maximum or minimum for constant
pressure, when the above condition in regard to the composition of
the coexistent phases is satisfied. The series of simultaneous values
of t and p for which the condition is satisfied separates those simul-
taneous values of t and p for which three coexistent phases are
not possible, from those for which there are two triads of coexistent
phases. These propositions may be extended to higher values of n}
and illustrated by the boiling temperatures and pressures of saturated
solutions of n — 2 different solids in solvents having two independently
variable components.
Internal Stability of Homogeneous Fluids as indicated by
Fundamental Equations.
We will now consider the stability of a fluid enclosed in a rigid
envelop which is non-conducting to heat and impermeable to all the
components of the fluid. The fluid is supposed initially homogeneous
in the sense in which we have before used the word, i.e., uniform in
every respect throughout its whole extent. Let Sv 82> ...Sn be the
ultimate components of the fluid ; we may then consider every body
which can be formed out of the fluid to be composed of 8lt $2, . . . Sn,
and that in only one way. Let mp m2, . . . mn denote the quantities of
these substances in any such body, and let e, 77, v, denote its energy,
entropy, and volume. The fundamental equation for compounds of
8V S2, ... Sn, if completely determined, will give us all possible sets of
simultaneous values of these variables for homogeneous bodies.
Now, if it is possible to assign such values to the constants T, P,
Mv M2, ...Mn that the value of the expression
e - Tr\ + Pv - M1m1 - M2m2 . . , - Mnmn (133)
shall be zero for the given fluid, arid shall be positive for every other
phase of the same components, i.e., for every homogeneous body*
not identical in nature and state with the given fluid (but composed
entirely of Slf $2, . . . Sn), the condition of the given fluid will be
stable.
For, in any condition whatever of the given mass, whether or not
homogeneous, or fluid, if the value of the expression (133) is not
* A vacuum is throughout this discussion to be regarded as a limiting case of an
extremely rarified body. We may thus avoid the necessity of the specific mention of
a vacuum in propositions of this kind.
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 101
negative for any homogeneous part of the mass, its value for the
whole mass cannot be negative; and if its value cannot be zero for
any homogeneous part which is not identical in phase with the mass
in its given condition, its value cannot be zero for the whole except
when the whole is in the given condition. Therefore, in the case
supposed, the value of this expression for any other than the given
condition of the mass is positive. (That this conclusion cannot be
invalidated by the fact that it is not entirely correct to regard a
composite mass as made up of homogeneous parts having the same
properties in respect to energy, entropy, etc., as if they were parts
of larger homogeneous masses, will easily appear from considerations
similar to those adduced on pages 77-78.) If, then, the value of
the expression (133) for the mass considered is less when it is in the
given condition than when it is in any other, the energy of the mass
in its given condition must be less than in any other condition in
which it has the same entropy and volume. The given condition is
therefore stable. (See page 57.)
Again, if it is possible to assign such values to the constants in
(133) that the value of the expression shall be zero for the given
fluid mass, and shall not be negative for any phase of the same
components, the given condition will be evidently not unstable. (See
page 57.) It will be stable unless it is possible for the given matter
in the given volume and with the given entropy to consist of homo-
geneous parts for all of which the value of the expression (133) is
zero, but which are not all identical in phase with the mass in its
given condition. (A mass consisting of such parts would be in
equilibrium, as we have already seen on pages 78, 79.) In this
case, if we disregard the quantities connected with the surfaces
which divide the homogeneous parts, we must regard the given
condition as one of neutral equilibrium. But in regard to these
homogeneous parts, which we may evidently consider to be all
different phases, the following conditions must be satisfied. (The.
accents distinguish the letters referring to the different parts, and
the unaccented letters refer to the whole mass.)
rf+n" + etc. = */,
v'+t/'+etc. = v,
m1/+m1//H-etc. = m1, - (134)
m2' -h mz" + etc. = ra2,
etc.
Now the values of rj, v, m1, m2, etc., are determined by the whole
fluid mass in its given state, and the values of -, -^>, etc., — f, — TT
, „ v v v v
etc., — f, — £-, etc., etc., are determined by the phases of the various
102 EQUILIBKIUM OF HETEROGENEOUS SUBSTANCES.
parts. But the phases of these parts are evidently determined by
the phase of the fluid as given. They form, in fact, the whole set of
coexistent phases of which the latter is one. Hence, we may regard
(134) as n -f 2 linear equations between v't v", etc. (The values of
v', v", etc., are also subject to the condition that none of them can be
negative.) Now one solution of these equations must give us the
given condition of the fluid; and it is not to be expected that they
will be capable of any other solution, unless the number of different
homogeneous parts, that is, the number of different coexistent phases,
is greater than 7i + 2. We have already seen (page 97) that it is
not probable that this is ever the case.
We may, however, remark that in a certain sense an infinitely large
fluid mass will be in neutral equilibrium in regard to the formation
of the substances, if such there are, other than the given fluid, for
which the value of (133) is zero (when the constants are so deter-
mined that the value of the expression is zero for the given fluid,
and not negative for any substance); for the tendency of such a
formation to be reabsorbed will diminish indefinitely as the mass
out of which it is formed increases.
When the substances 8lf S2, . . . Sn are all independently variable
components of the given mass, it is evident from (86) that the con-
ditions that the value of (133) shall be zero for the mass as given,
and shall not be negative for any phase of the same components,
can only be fulfilled when the constants T, P, Mv M2, . . . Mn are equal
to the temperature, the pressure, and the several potentials in the
given mass. If we give these values to the constants, the expression
(133) will necessarily have the value zero for the given mass, and we
shall only have to inquire whether its value is positive for all other
phases. But when 8V S2, ... Sn are not all independently variable
components of the given mass, the values which it will be necessary
to give to the constants in (133) cannot be determined entirely from
the properties of the given mass ; but T and P must be equal to its
temperature and pressure, and it will be easy to obtain as many
equations connecting Mv M2, . . . Mn with the potentials in the given
mass as it contains independently variable components.
When it is not possible to assign such values to the constants in
(133) that the value of the expression shall be zero for the given fluid,
and either zero or positive for any phase of the same components,
we have already seen (pages 75-79) that if equilibrium subsists
without passive resistances to change, it must be in virtue of pro-
perties which are peculiar to small masses surrounded by masses
of different nature, and which are not indicated by fundamental
equations. In this case, the fluid will necessarily be unstable, if we
extend this term to embrace all cases in which an initial disturbance
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 103
confined to a small part of an indefinitely large fluid mass will cause
an ultimate change of state not indefinitely small in degree throughout
the whole mass. In the discussion of stability as indicated by funda-
mental equations it will be convenient to use the term in this sense.*
In determining for any given positive values of T and P and any
given values whatever of Mv M2, ... Mn whether the expression (133)
is capable of a negative value for any phase of the components
8lf S2, ... Sn, and if not, whether it is capable of the value zero for
any other phase than that of which the stability is in question, it
is only necessary to consider phases having the temperature T and
pressure P. For we may assume that a mass of matter represented
by any values of mv ra2, . . . mn is capable of at least one state of
not unstable equilibrium (which may or may not be a homogeneous
state) at this temperature and pressure. It may easily be shown
that for such a state the value of e — Ttj + Pv must be as small as
for any other state of the same matter. The same will therefore be
true of the value of (133). Therefore if this expression is capable of
a negative value for any mass whatever, it will have a negative value
for that mass at the temperature T and pressure P. And if this mass
is not homogeneous, the value of (133) must be negative for at least
one of its homogeneous parts. So also, if the expression (133) is not
capable of a negative value for any phase of the components, any
phase for which it has the value zero must have the temperature T
and the pressure P.
*If we wish to know the stability of the given fluid when exposed to a constant tem-
perature, or to a constant pressure, or to both, we have only to suppose that there is
enclosed in the same envelop with the given fluid another body (which cannot combine
with the fluid) of which the fundamental equation is e = TTJ, or e= — Pv, or €=Ttj- Pv,
as the case may be (T and P denoting the constant temperature and pressure, which
of course must be those of the given fluid), and to apply the criteria of page 57 to
the whole system. When it is possible to assign such values to the constants in
(133) that the value of the expression shall be zero for the given fluid and positive
for every other phase of the same components, the value of (133) for the whole system
will be less when the system is in its given condition than when it is in any other.
(Changes of form and position of the given fluid are of course regarded as immaterial. )
Hence the fluid is stable. When it is not possible to assign such values to the con-
stants that the value of (133) shall be zero for the given fluid and zero or positive for
any other phase, the fluid is of course unstable. In the remaining case, when it is
possible to assign such values to the constants that the value of (133) shall be zero
for the given fluid and zero or positive for every other phase, but not without the
value zero for some other phase, the state of equilibrium of the fluid as stable or
neutral will be determined by the possibility of satisfying, for any other than the
given condition of the fluid, equations like (134), in which, however, the first or the
second or both are to be stricken out, according as we are considering the stability
of the fluid for constant temperature, or for constant pressure, or for both. The
number of coexistent phases will sometimes exceed by one or two the number of the
remaining equations, and then the equilibrium of the fluid will be neutral in respect
to one or two independent changes.
104 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
It may easily be shown that the same must be true in the limiting
cases in which T=0 and P = 0. For negative values of P, (133) is
always capable of negative values, as its value for a vacuum is Pv.
For any body of the temperature T and pressure P, the expression
(133) may by (91) be reduced to the form
f — Mjn^ - M2m2 . . . - Mnmn. (135)
We have already seen (page 77) that an expression like (133),
when T, P, Mv M2, . . . Mn and v have any given finite values,
cannot have an infinite negative value as applied to any real body.
Hence, in determining whether (133) is capable of a negative value
for any phase of the components $lt $2, . . . Sn, and if not, whether it is
capable of the value zero for any other phase than that of which the
stability is in question, we have only to consider the least value of
which it is capable for a constant value of v. Any body giving this
value must satisfy the condition that for constant volume
de-Tdij — Mldml-Mtdmt...-Mndmn^.O, (136)
or, if we substitute the value of de taken from equation (86), using
subscript a ... g for the quantities relating to the actual components
of the body, and subscript h . . . k for those relating to the possible,
tdr) + /uLadma...+juLgdmg+jULhdmh...+/jLkdmk
-Tdrj-Mldml-M2dm2...-Mndmn^0. (137)
That is, the temperature of the body must be equal to T, and the
potentials of its components must satisfy the same conditions as if it
were in contact and in equilibrium with a body having potentials
Mlt M2, . . . Mn. Therefore the same relations must subsist between
fj.a . . . fJLg) and Ml ... Mn as between the units of the corresponding
substances, so that
*
majULa... + mg/uLg = mlMl...+mnMn; (138)
and as we have by (93)
e = trj-pv+juiama... -\-fjigmg, (139)
the expression (133) will reduce (for the body or bodies for which it
has the least value per unit of volume) to
(P-p)v, (HO)
the value of which will be positive, null, or negative, according as the
value of
P-p (141)
is positive, null, or negative.
Hence, the conditions in regard to the stability of a fluid of which
all the ultimate components are independently variable admit a very
simple expression. If the pressure of the fluid is greater than that
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 105
of any other phase of the same components which has the same
temperature and the same values of the potentials for its actual
components, the fluid is stable without coexistent phases; if its
pressure is not as great as that of some other such phase, it will
be unstable; if its pressure is as great as that of any other such
phase, but not greater than that of every other, the fluid will
certainly not be unstable, and in all probability it will be stable
(when enclosed in a rigid envelop which is impermeable to heat
and to all kinds of matter), but it will be one of a set of coexistent
phases of which the others are the phases which have the same
pressure.
The considerations of the last two pages, by which the tests relating
to the stability of a fluid are simplified, apply to such bodies as
actually exist. But if we should form arbitrarily any equation as a
fundamental equation, and ask whether a fluid of which the pro-
perties were given by that equation would be stable, the tests of
stability last given would be insufficient, as some of our assumptions
might not be fulfilled by the equation. The test, however, as first
given (pages 100-102) would in all cases be sufficient.
Stability in respect to Continuous Changes of Phase.
In considering the changes which may take place in any mass, we
have already had occasion to distinguish between infinitesimal changes
in existing phases, and the formation of entirely new phases. A
phase of a fluid may be stable in regard to the former kind of change,
and unstable in regard to the latter. In this case it may be capable
of continued existence in virtue of properties which prevent the com-
mencement of discontinuous changes. But a phase which is unstable
in regard to continuous changes is evidently incapable of permanent
existence on a large scale except in consequence of passive resistances
to change. We will now consider the conditions of stability in respect
to continuous changes of phase, or, as it may also be called, stability
in respect to adjacent phases. We may use the same general test as
before, except that the expression (133) is to be applied only to phases
which differ infinitely little from the phase of which the stability is
in question. In this case the component substances to be considered
will be limited to the independently variable components of the fluid,
and the constants Mv Mz, etc., must have the values of the potentials
for these components in the given fluid. The constants in (133) are
thus entirely determined and the value of the expression for the
given phase is necessarily zero. If for any infinitely small variation
of the phase the value of (133) can become negative, the fluid will
be unstable ; but if for every infinitely small variation of the phase
the value of (133) becomes positive, the fluid will be stable. The only
106 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
remaining case, in which the phase can be varied without altering the
value of (133) can hardly be expected to occur. The phase concerned
would in such a case have coexistent adjacent phases. It will be
sufficient to discuss the condition of stability (in respect to continuous
changes) without coexistent adjacent phases.
This condition, which for brevity's sake we will call the condition
of stability, may be written in the form
e"-tftf'+pV'-fr'ml''...-fjLn'mn" > 0, (142)
in which the quantities relating to the phase of which the stability is
in question are distinguished by single accents, and those relating
to the other phase by double accents. This condition is by (93)
equivalent to
w' > 0, (143)
and to
-t'n" +P'V" - pW . ..-//>„"
" > 0. (144)
The condition (143) may be expressed more briefly in the form
Ae>£A?7 — pAv+fj.l^ml... + /zwAmn, (145)
if we use the character A to signify that the condition, although
relating to infinitesimal differences, is not to be interpreted in accord-
ance with the usual convention in respect to differential equations
with neglect of infinitesimals of higher orders than the first, but is
to be interpreted strictly, like an equation between finite differences.
In fact, when a condition like (145) (interpreted strictly) is satisfied
for infinitesimal differences, it must be possible to assign limits within
which it shall hold true of finite differences. But it is to be remem-
bered that the condition is not to be applied to any arbitrary values
of A^, Av, Am1} . . . Amn, but only to such as are determined by a
change of phase. (If only the quantity of the body which determines
the value of the variables should vary and not its phase, the value of
the first member of (145) would evidently be zero.) We may free
ourselves from this limitation by making v constant, which will cause
the term —pAv to disappear. If we then divide by the constant v,
the condition will become
, (146)
v v v v
in which form it will not be necessary to regard v as constant. As
we may obtain from (86)
V V V V
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 107
we see that the stability of any phase in regard to continuous changes
depends upon the same conditions in regard to the second and higher
differential coefficients of the density of energy regarded as a function
of the density of entropy and the densities of the several components^
which would make the density of energy a minimum,, if the necessary
conditions in regard to the first differential coefficients were fulfilled.
When n = l, it may be more convenient to regard m as constant
in (145) than v. Regarding m a constant, it appears that the stability
of a phase depends upon the same conditions in regard to the second
and higher differential coefficients of the energy of a unit of mass
regarded as a function of its entropy and volume, which would make
the energy a minimum, if the necessary conditions in regard to the
first differential coefficients were fulfilled.
The formula (144) expresses the condition of stability for the phase
to which t', p, etc., relate. But it is evidently the necessary and
sufficient condition of the stability of all phases of certain kinds of
matter, or of all phases within given limits, that (144) shall hold true
of any two infinitesimally differing phases within the same limits, or,
as the case may be, in general. For the purpose, therefore, of such
collective determinations of stability, we may neglect the distinction
between the two states compared, and write the condition in the form
... -mnA/zn>0, (148)
or Ap> -A^ + TiA/u1... -\ — -A/*n. (149)
Comparing (98), we see that it is necessary and sufficient for the
stability in regard to continuous changes of all the phases within any
given limits, that within those limits the same conditions should be
fulfilled in respect to the second and higher differential coefficients
of the pressure regarded as a function of the temperature and the
several potentials, which would make the pressure a minimum, if
the necessary conditions with respect to the first differential co-
efficients were fulfilled.
By equations (87) and (94), the condition (142) may be brought to
the form
mn' > 0. (150)
For the stability of all phases within any given limits it is necessary
and sufficient that within the same limits this condition shall hold
true of any two phases which differ infinitely little. This evidently
requires that when v' = v", m^ = m^f, ... mn' = m
n,
(151)
108 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
and that when t' — t"
Tj,"+p'v"-vl'ml"...+fin'mn"
— \l/ —p'v' -j- ^-iffii ... -f-//w'mn'> 0. (152)
These conditions may be written in the form
(153)
<>0, (154)
in which the subscript letters indicate the quantities which are to
be regarded as constant, m standing for all the quantities mx . . . mn.
If these conditions hold true within any given limits, (150) will also
hold true of any two infinitesimally differing phases within the same
limits. To prove this, we will consider a third phase, determined by
the equations
t" = tf, (155)
and v'" = v", m/" = m/', . . . mn'" = m/. (156)
Now by (153), \!s'"-\ls"+(t'"-t")ri" <0; (157)
and by (154), \/r"'+ p'v'" — jJ-{m-{" ... — Hnmn"
— \l/ —p'v' +/*1/m1/ ... -\-ju.n'mn'>Q. (158)
Hence, \fr" + 1" q" +p'vf" - /ij'm/" ... - fJLn'mn'"
which by v(1^5) and (156) is equivalent to (150). Therefore, the
conditions (153) and (154) in respect to the phases within any given
limits are necessary and sufficient for the stability of all the phases
within those limits. It will be observed that in (153) we have the
condition of thermal stability of a body considered as unchange-
able in composition and in volume, and in (154), the condition of
mechanical and chemical stability of the body considered as main-
tained at a constant temperature. Comparing equation (88), we see
that the condition (153) will be satisfied, if -r™r<0, i.e., if -^ or t-A
(the specific heat for constant volume) is positive. When n = l, i.e.,
when the composition of the body is invariable, the condition (154)
will evidently not be altered, if we regard m as constant, by which
the condition will be reduced to
(160)
This condition will evidently be satisfied if -r^r>0, i.e., if — £•
* dv2 dv
Off)
or — v-f- (the elasticity for constant temperature) is positive. But
when n > 1, (154) may be abbreviated more symmetrically by making
v constant.
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 109
Again, by (91) and (96), the condition (142) may be brought to
the form
-f -f^+pV+ftX' ». + M.X'>0. (161)
Therefore, for the stability of all phases within any given limits it is
necessary and sufficient that within the same limits
[AM-*A*-vAp]w<0, (162)
and [Af-ftAm,... -//nAmn]fil>>0, (163)
as may easily be proved by the method used with (153) and (154).
The first of these formulae expresses the thermal and mechanical
conditions of stability for a body considered as unchangeable in
composition, and the second the conditions of chemical stability for
a body considered as maintained at a constant temperature and
pressure. If n = l, the second condition falls away, and as in this
case f =mfJL, condition (162) becomes identical with (148).
The foregoing discussion will serve to illustrate the relation of the
general condition of stability in regard to continuous changes to
some of the principal forms of fundamental equations. It is evident
that each of the conditions (146), (149), (154), (162), (163) involves
in general several particular conditions of stability. We will now
give our attention to the latter. Let
$ = € - t'l\ +p'v - yM^i ... - t*n'mn> (164)
the accented letters referring to one phase and the unaccented to
another. It is by (142) the necessary and sufficient condition of the
stability of the first phase that, for constant values of the quantities
relating to that phase and of v, the value of <3? shall be a minimum
when the second phase is identical with the first. Differentiating
(164), we have by (86)
d3> = (t-t')dn-(p-p')dv + (fjil-Hl')dm1... +(fjLn-fjLn')dmn. (165)
Therefore, the above condition requires that if we regard v, m1? . . . mn
as having the constant values indicated by accenting these letters,
t shall be an increasing function of q, when the variable phase differs
sufficiently little from the fixed. But as the fixed phase may be any
one within the limits of stability, t must be an increasing function
of i\ (within these limits) for any constant values of v , m^ . . . mn.
This condition may be written
(—} >0. (166)
\{\1]/ Vf mi} ... mn
When this condition is satisfied, the value of 4>, for any given values
of v, mv . . . mn, will be a minimum when t = t'. And therefore, in
applying the general condition of stability relating to the value of
3>, we need only consider the phases for which t = tf.
110 EQUILIBKIUM OF HETEROGENEOUS SUBSTANCES.
We see again by (165) that the general condition requires that
if we regard t, v, m2, . . . mn as having the constant values indicated
by accenting these letters, yux shall be an increasing function of mlr
when the variable phase differs sufficiently little from the fixed. But
as the fixed phase may be any one within the limits of stability, //i
must be an increasing function of mx (within these limits) for any
constant values of t, v, m2, . . . mn. That is,
>0. (167)
tf Vj Wl2) ... ^
When this condition is satisfied, as well as (166), $ will have a
minimum value, for any constant values of v, m2, . . . mn, when t — tf
and /*! = //!'; so that in applying the general condition of stability
we need only consider the phases for which t = t' and JJL^ = ///.
In this way we may also obtain the following particular conditions
of stability :
>0> (168>
mn
><>. (169)
^, ...,,„_,
When the n + 1 conditions (166)-(169) are all satisfied, the value
of $, for any constant value of v, will be a minimum when the tem-
perature and the potentials of the variable phase are equal to those
of the fixed. The pressures will then also be equal and the phases
will be entirely identical. Hence, the general condition of stability
will be completely satisfied, when the above particular conditions are
satisfied.
From the manner in which these particular conditions have been
derived, it is evident that we may interchange in them r\, mt, . . . mn
in any way, provided that we also interchange in the same way
t, fjiv ... fJLn. In this way we may obtain different sets of n+1
conditions which are necessary and sufficient for stability. The
quantity v might be included in the first of these lists, and — p in
the second, except in cases when, in some of the phases considered,
the entropy or the quantity of one of the components has the value
zero. Then the condition that that quantity shall be constant would
create a restriction upon the variations of the phase, and cannot be
substituted for the condition that the volume shall be constant in
the statement of the general condition of stability relative to the
minimum value of $.
To indicate more distinctly all these particular conditions at once,
we observe that the condition (144), and therefore also the condition
obtained by interchanging the single and double accents, must hold
EQUILTBEIUM OF HETEROGENEOUS SUBSTANCES. Ill
true of any two infinitesimally differing phases within the limits of
stability. Combining these two conditions we have
(170)
which may be written more briefly
AtfA;/ — Ap Av+A/^Amj ... + A/znAmn>0. (171)
This must hold true of any two infinitesimally differing phases within
the limits of stability. If, then, we give the value zero to one of
the differences in every term except one, but not so as to make the
phases completely identical, the values of the two differences in the
remaining term will have the same sign, except in the case of A/>
and A-y, which will have opposite signs. (If both states are stable
this will hold true even on the limits of stability.) Therefore, within
the limits of stability, either of the two quantities occurring (after the
sign A) in any term of (171) is an increasing function of the other, —
except p and v, of which the opposite is true, — when we regard as
constant one of the quantities occurring in each of the other terms,
but not such as to make the phases identical.
If we write d for A in (166)-(169), we obtain conditions which
are always sufficient for stability. If we also substitute ^ for >, we
obtain conditions which are necessary for stability. Let us consider
the form which these conditions will take when rj, v, mv . . . ran are
regarded as independent variables. When dv — Q, we shall have
dt
dt
dt ,
j — dmn
dm
(172)
Let us write Rn+1 for the determinant of the order n + 1
^dri ' dmndrj
dr] d
(173)
dt]dmn dmldmn'
of which the constituents are by (86) the same as the coefficients in
equations (172), and Rn, Rn_v etc., for the minors obtained by erasing
the last column and row in the original determinant and in the
112 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
minors successively obtained, and R1 for the last remaining con-
stituent. Then if dt, dfJLv...djuLn_v and dv all have the value zero,
we have by (172)
= Rn+ldmn> (174)
that is, - =i. (175)
\<fr
In like manner we obtain
etc.
Therefore, the conditions obtained by writing d for A in (166)-(169)
are equivalent to this, that the determinant given above with the n
minors obtained from it as above mentioned and the last remaining
d2e
constituent -^ shall all be positive. Any phase for which this con-
dition is satisfied will be stable, and no phase will be stable for
which any of these quantities has a negative value. But the con-
ditions (166)-(169) will remain valid, if we interchange in any way
TI, mp . . . mn (with corresponding interchange of t, fa, ... JUL^. Hence
the order in which we erase successive columns with the corresponding
rows in the determinant is immaterial. Therefore none of the minors
of the determinant (173) which are formed by erasing corresponding
rows and columns, and none of the constituents of the principal
diagonal, can be negative for a stable phase.
We will now consider the conditions which characterize the'limifa
of stability (i.e., the limits which divide stable from unstable phases)
with respect to continuous changes.* Here, evidently, one of the
conditions (166)-(169) must cease to hold true. Therefore, one of
the differential coefficients formed by changing A into d in the first
members of these conditions must have the value zero. (That it is
the numerator and not the denominator in the differential coefficient
which vanishes at the limit appears from the consideration that the
denominator is in each case the differential of a quantity which is
necessarily capable of progressive variation, so long at least as the
phase is capable of variation at all under the conditions expressed
by the subscript letters.) The same will hold true of the set of
differential coefficients obtained from these by interchanging in any
way T], mv . . . mn, and simultaneously interchanging t, fJLv ... jmn in the
same way. But we may obtain a more definite result than this.
* The limits of stability with respect to discontinuous changes are formed by phases
which are coexistent with other phases. Some of the properties of such phases have
already been considered. See pages 96-100.
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 113
Let us give to r\ or t, to ml or fjLv ...to mn_1 or /zn_1} and to v,
the constant values indicated by these letters when accented. Then
by (165)
(177)
Now *-<
approximately, the differential coefficient being interpreted in accord-
ance with the above assignment of constant values to certain variables,
and its value being determined for the phase to which the accented
letters refer. Therefore,
'.-<)*»* (179)
and * = i(m"-7n"/)2- (180)
The quantities neglected in the last equation are evidently of the
same order as (wn — wn')s. Now this value of $ will of course be
different (the differential coefficient having a different meaning)
according as we have made i\ or t constant, and according as we have
made mx or ^ constant, etc. ; but since, within the limits of stability,
the value of <3>, for any constant values of mn and v, will be the least
when t, p, /*!>• ••/*„-! have the values indicated by accenting these
letters, the value of the differential coefficient will be at least as small
when we give these variables these constant values, as when we
adopt any other of the suppositions mentioned above in regard to
the quantities remaining constant. And in all these relations we
may interchange in any way T/, mp . . . mn if we interchange in the
same way t, [tv... fJLn. It follows that, within the limits of stability,
when we choose for any one of the differential coefficients
drf dml'"'dmn
the quantities following the sign d in the numerators of the others
together with v as those which are to remain constant in differen-
tiation, the value of the differential coefficient as thus determined
will be at least as small as when one or more of the constants in
differentiation are taken from the denominators, one being still taken
from each fraction, and v as before being constant.
Now we have seen that none of these differential coefficients, as
determined in any of these ways, can have a negative value within
the limit of stability, and that some of them must have the value zero
at that limit. Therefore in virtue of the relations just established,
one at least of these differential coefficients determined by considering
G. i. H
114 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
constant the quantities occurring in the numerators of the others
together with v, will have the value zero. But if one such has the
value zero, all such will in general have the same value. For if
for example, has the value zero, we may change the density of the
component Sn without altering (if we disregard infinitesimals of
higher orders than the first) the temperature or the potentials, and
therefore, by (98), without altering the pressure. That is, we may
change the phase without altering any of the quantities t, p, fJ.v ... /J.n.
(In other words, the phases adjacent to the limits of stability exhibit
approximately the relations characteristic of neutral equilibrium.)
Now this change of phase, which changes the density of one of
the components, will in general change the density of the others
and the density of entropy. Therefore, all the other differential
coefficients formed after the analogy of (182), i.e., formed from the
fractions in (181) by taking as constants for each the quantities in
the numerators of the others together with v, will in general have
the value zero at the limit of stability. And the relation which
characterizes the limit of stability may be expressed, in general, by
setting any one of these differential coefficients equal to zero. Such
an equation, when the fundamental equation is known, may be
reduced to the form of an equation between the independent variables
of the fundamental equation.
Again, as the determinant (173) is equal to the product of the
differential coefficients obtained by writing d for A in the first
members of (166)-(169), the equation of the limit of stability may be
expressed by setting this determinant equal to zero. The form of
the differential equation as thus expressed will not be altered by the
interchange of the expressions q, ml,...inn> but it will be altered
by the substitution of v for any one of these expressions, which will
be allowable whenever the quantity for which it is substituted has
not the value zero in any of the phases to which the formula is to
be applied.
The condition formed by setting the expression (182) equal to
zero is evidently equivalent to this, that
I ^Mw I /\ /i oo\
I — • — I =0, (loo)
that is, that
I — I
(184)
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 115
or by (98), if we regard t, JULV ... //n as the independent variables,
In like manner we may obtain
z /1QC,
' (186)
Any one of these equations, (185), (186), may be regarded, in general,
as the equation of the limit of stability. We may be certain that
at every phase at that limit one at least of these equations will
hold true.
Geometrical Illustrations.
Surfaces in which the Composition of the Body represented is
Constant.
In the second paper of this volume (pp. 33-54) a method is
described of representing the thermodynamic properties of substances
of invariable composition by means of surfaces. The volume, entropy,
and energy of a constant quantity of a substance are represented
by rectangular co-ordinates. This method corresponds to the first
kind of fundamental equation described on pages 85-89. Any
other kind of fundamental equation for a substance of invariable
composition will suggest an analogous geometrical method. Thus,
if we make m constant, the variables in any one of the sets (99)-(103)
are reduced to three, which may be represented by rectangular
co-ordinates. This will, however, afford but four different methods,
for, as has already (page 94) been observed, the two last sets are
essentially equivalent when n — \.
The first of the above mentioned methods has certain advantages,
especially for the purposes of theoretical discussion, but it may
often be more advantageous to select a method in which the proper-
ties represented by two of the co-ordinates shall be such as best serve
to identify and describe the different states of the substance. This
condition is satisfied by temperature and pressure as well, perhaps,
as by any other properties. We may represent these by two of
the co-ordinates and the potential by the third. (See page 88.)
It will not be overlooked that there is the closest analogy between
these three quantities in respect to their parts in the general
theory of equilibrium. (A similar analogy exists between volume,
entropy, and energy.) If we give m the constant value unity,
the third co-ordinate will also represent f, which then becomes equal
to /UL.
116 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
Comparing the two methods, we observe that in one
v = x, rj = y, e = zt (187)
dz dz . dz dz /IQQ\
P- ~& t=^' * = *-*-&*- dyy ' (188)
and in the other
t = x,p = y, !* = £=*, (189)
dz dz dz dz
n=—-j->v='j->€=z—^-x—j~y'
dx dy dx dyy
Now -=- and -r- are evidently determined by the inclination of the
y dz dz
tangent plane, and z—-j-x—-j-y is the segment which it cuts off
on the axis of Z. The two methods, therefore, have this reciprocal
relation, that the quantities represented in one by the position of
a point in a surface are represented in the other by the position
of a tangent plane.
The surfaces defined by equations (187) and (189) may be dis-
tinguished as the v-fj-e surface, and the t-p-£ surface, of the substance
to which they relate.
In the t-p-£ surface a line in which one part of the surface cuts
another represents a series of pairs of coexistent states. A point
through which pass three different parts of the surface represents a
triad of coexistent states. Through such a point will evidently pass
the three lines formed by the intersection of these sheets taken two
by two. The perpendicular projection of these lines upon the p-t
plane will give the curves which have recently been discussed by
Professor J. Thomson.* These curves divide the space about the
projection of the triple point into six parts which may be dis-
tinguished as follows : Let f (v}, £(L\ £(s) denote the three ordinates
determined for the same values of p and t by the three sheets passing
through the triple point, then in one of the six spaces
?"<?»<?», (191)
in the next space, separated from the former by the line for which
ML) _ «S)
, f<n < £W < £*>, (192)
in the third space, separated from the last by the line for which
in the fourth f(5) < f(L> < f<r>, (194)
in the fifth £™ < £«n < £<n (195)
in the sixth fw < f(r> < ?*>. (196)
* See the Reports of the British Association for 1871 and 1872 ; and Philosophical
Magazinet vol. xlvii. (1874), p. 447.
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 117
The sheet which gives the least values of f is in each case that which
represents the stable states of the substance. From this it is evident
that in passing around the projection of the triple point we pass
through lines representing alternately coexistent stable and coexistent
unstable states. But the states represented by the intermediate
values of f may be called stable relatively to the states represented
by the highest. The differences QL) — QV\ etc. represent the amount
of work obtained in bringing the substance by a reversible process
from one to the other of the states to which these quantities relate,
in a medium having the temperature and pressure common to the
two states. To illustrate such a process, we may suppose a plane
perpendicular to the axis of temperature to pass through the points
representing the two states. This will in general cut the double line
formed by the two sheets to which the symbols (L) and (V) refer.
The intersections of the plane with the two sheets will connect the
double point thus determined with the points representing the initial
and final states of the process, and thus form a reversible path for the
body between those states.
The geometrical relations which indicate the stability of any state
may be easily obtained by applying the principles stated on pp. 100 ff.
to the case in which there is but a single component. The expression
(133) as a test of stability will reduce to
•
e-t'q+p'v-fJL'm, (197)
the accented letters referring to the state of which the stability is in
question, and the unaccented letters to any other state. If we consider
the quantity of matter in each state to be unity, this expression may
be reduced by equations (91) and (96) to the form
£-£'+(t-t')q-(p-p')v, (198)
which evidently denotes the distance of the point (£', p', f ') below the
tangent plane for the point (t, p, f), measured parallel to the axis of £
Hence if the tangent plane for every other state passes above the
point representing any given state, the latter will be stable. If any
of the tangent planes pass below the point representing the given
state, that state will be unstable. Yet it is not always necessary to
consider these tangent planes. For, as has been observed on page 103,
we may assume that (in the case of any real substance) there will
be at least one not unstable state for any given temperature and
pressure, except when the latter is negative. Therefore the state
represented by a point in the surface on the positive side of the
plane p = 0 will be unstable only when there is a point in the surface
for which t and p have the same values and f a less value. It follows
from what has been stated, that where the surface is doubly convex
118 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
upwards (in the direction in which f is measured) the states repre-
sented will be stable in respect to adjacent states. This also appears
directly from (162). But where the surface is concave upwards in
either of its principal curvatures the states represented will be un-
stable in respect to adjacent states.
When the number of component substances is greater than unity,
it is not possible to represent the fundamental equation by a single
surface. We have therefore to consider how it may be represented
by an infinite number of surfaces. A natural extension of either of
the methods already described will give us a series of surfaces in
which every one is the v-ij-e surface, or every one the t-p-£ surface for
a body of constant composition, the proportion of the components
varying as we pass from one surface to another. But for a simul-
taneous view of the properties which are exhibited by compounds of
two or three components without change of temperature or pressure,
we may more advantageously make one or both of the quantities
t or p constant in each surface.
Surfaces and Curves in which the Composition of the Body repre-
sented is Variable and its Temperature and Pressure are
Constant.
When there are three components, the position of a point in the
X-Y plane may indicate the composition of a body most simply,
perhaps, as follows. The body is supposed to be composed of the
quantities m1? m2, ra3 of the substances Sv S2, SB, the value of
r^-f m2+m3 being unity. Let PI} P2, P3 be any three points in the
plane, which are not in the same straight line. If we suppose masses
equal to mv ra2, m3 to be placed at these three points, the center of
gravity of these masses will determine a point which will indicate
the value of these quantities. If the triangle is equiangular and has
the height unity, the distances of the point from the three sides will
be equal numerically to mv m2, m3. Now if for every possible phase
of the components, of a given temperature and pressure, we lay off
from the point in the X-Y plane which represents the composition
of the phase a distance measured parallel to the axis of Z and repre-
senting the value of f (when m1+m2-|-m3 = l), the points thus
determined will form a surface, which may be designated us the
m1-i7i2-m3-f surface of the substances considered, or simply as their
m-f surface, for the given temperature and pressure. In like manner,
when there are but two component substances, we may obtain a
curve, which we will suppose in the X-Z plane. The coordinate y
may then represent temperature or pressure. But we will limit
ourselves to the consideration of the properties of the m-f surface
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 119
for n = 3, or the m-f curve for n = 2, regarded as a surface, or curve,
which varies with the temperature and pressure.
As by (96) and (92)
and (for constant temperature and pressure)
if we imagine a tangent plane for the point to which these letters
relate, and denote by f the ordinate for any point in the plane, and
by w/, ra27, w87, the distances of the foot of this ordinate from the
three sides of the triangle PjPgPg, we may easily obtain
which we may regard as the equation of the tangent plane. Therefore
the ordinates for this plane at Pp P2, and P3 are equal respectively
to the potentials JJLV yu2, fa- And in general, the ordinate for any point
in the tangent plane is equal to the potential (in the phase represented
by the point of contact) for a substance of which the composition is
indicated by the position of the ordinate. (See page 93.) Among
the bodies which may be formed of Sv S2, and SB, there may be some
which are incapable of variation in composition, or which are capable
only of a single kind of variation. These will be represented by
single points and curves in vertical planes. Of the tangent plane to
one of these curves only a single line will be fixed, which will deter-
mine a series of potentials of which only two will be independent.
The phase represented by a separate point will determine only a
single potential, viz., the potential for the substance of the body itself,
which will be equal to f
The points representing a set of coexistent phases have in general
a common tangent plane. But when one of these points is situated
on the edge where a sheet of the surface terminates, it is sufficient if
the plane is tangent to the edge and passes below the surface. Or,
when the point is at the end of a separate line belonging to the
surface, or at an angle in the edge of a sheet, it is sufficient if the
plane pass through the point and below the line or sheet. If no part
of the surface lies below the tangent plane, the points where it meets
the plane will represent a stable (or at least not unstable) set of
coexistent phases.
The surface which we have considered represents the relation
between f and mv w2, m8 for homogeneous bodies when t and p
have any constant values and m1+m2+m3=l. It will often be
useful to consider the surface which represents the relation between
the same variables for bodies which consist of parts in different but
coexistent phases. We may suppose that these are stable, at least in
120 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
regard to adjacent phases, as otherwise the case would be devoid of
interest. The point which represents the state of the composite
body will evidently be at the center of gravity of masses equal to
the parts of the body placed at the points representing the phases
of these parts. Hence from the surface representing the properties
of homogeneous bodies, which may be called the primitive surface, we
may easily construct the surface representing the properties of bodies
which are in equilibrium but not homogeneous. This may be called
the secondary or derived surface. It will consist, in general, of various
portions or sheets. The sheets which represent a combination of two
phases may be formed by rolling a double tangent plane upon the
primitive surface ; the part of the envelop of its successive positions
which lies between the curves traced by the points of contact will
belong to the derived surface. When the primitive surface has a
triple tangent plane or one of higher order, the triangle in the tangent
plane formed by joining the points of contact, or the smallest polygon
without re-entrant angles which includes all the points of contact, will
belong to the derived surface, and will represent masses consisting in
general of three or more phases.
Of the whole thermodynamic surface as thus constructed for any
temperature and any positive pressure, that part is especially im-
portant which gives the least value of f for any given values of
mv m2, m3. The state of a mass represented by a point in this part
of the surface is one in which no dissipation of energy would be
possible if the mass were enclosed in a rigid envelop impermeable
both to matter and to heat; and the state of any mass composed
of Sv S2, SB in any proportions, in which the dissipation of energy
has been completed, so far as internal processes are concerned (i.e.,
under the limitations imposed by such an envelop as above supposed),
would be represented by a point in the part which we are considering
of the m-f surface for the temperature and pressure of the mass. We
may therefore briefly distinguish this part of the surface as the surface
of dissipated energy. It is evident that it forms a continuous sheet,
the projection of which upon the X-Y plane coincides with the triangle
P1P2P3, (except when the pressure for which the m-£ surface is
constructed is negative, in which case there is no surface of dissipated
energy), that it nowhere has any convexity upward, and that the
states which it represents are in no case unstable.
The general properties of the m-f lines for two component
substances are so similar as not to require separate consideration.
We now proceed to illustrate the use of both the surfaces and the
lines by the discussion of several particular cases.
Three coexistent phases of two component substances may be
represented by the points A, B, and C, in figure 1, in which f is
\
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 121
measured toward the top of the page from Pj^, /ml toward the left
from P2Q2, and ra2 toward the right from PxQr It is supposed
that P1P2 = 1. Portions of the curves to which these points belong
are seen in the figure, and will be denoted by the symbols (A), (B),
(C). We may, for convenience, speak of these as separate curves,
without implying anything in regard to their possible continuity in
parts of the diagram remote from their common tangent AC. The
line of dissipated energy includes the straight line AC and portions
of the primitive curves (A) and (C). Let us first consider how the
diagram will be altered, if the temperature is varied while the
pressure remains constant. If the temperature receives the incre-
ment dt, an ordinate of which the position is fixed will receive
the increment (-77) dt, or — ydi. (The reader will easily convince
\C16 / p fn
himself that this is true of the ordinates for the secondary line AC,
as well as of the ordinates for the
primitive curves.) Now if we denote
by r\ the entropy of the phase repre-
sented by the point B considered as
belonging to the curve (B), and by rf
the entropy of the composite state of
the same matter represented by the
point B considered as belonging to
the tangent to the curves (A) and (C),
t(r( — r(') will denote the heat yielded by a unit of matter in passing
from the first to the second of these states. If this quantity is
positive, an elevation of temperature will evidently cause a part of
the curve (B) to protrude below the tangent to (A) and (C), which
will no longer form a part of the line of dissipated energy. This
line will then include portions of the three curves (A), (B), and (C)j
and of the tangents to (A) and (B) and to (B) and (C). On the
other hand, a lowering of the temperature will cause the curve (B)
to lie entirely above the tangent "to (A) and (C), so that all the
phases of the sort represented by (B) will be unstable. If t(rf — rj")
is negative, these effects will be produced by the opposite changes
of temperature.
The effect of a change of pressure while the temperature remains
constant may be found in a manner entirely analogous. The varia-
P,
b
PT
tion of any ordinate will be -r dp or vdp. Therefore, if the
\U>P't, m
volume of the homogeneous phase represented by the point B is
greater than the volume of the same matter divided between the
^phases represented by A and C, an increase of pressure will give a
diagram indicating that all phases of the sort represented by curve
122 EQUILIBBIUM OF HETEROGENEOUS SUBSTANCES.
(B) are unstable, and a decrease of pressure will give a diagram
indicating two stable pairs of coexistent phases, in each of which
one of the phases is of the sort represented by the curve (B). When
the relation of the volumes is the reverse of that supposed, these
results will be produced by the opposite changes of pressure.
When we have four coexistent phases of three component sub-
stances, there are two cases which must be distinguished. In the
first, one of the points of contact of the primitive surface with the
quadruple tangent plane lies within the triangle formed by joining
the other three; in the second, the four points may be joined so
as to form a quadrilateral without re-entrant angles. Figure 2
represents the projection upon the X-Y plane (in which mp m2, m3
are measured) of a part of the surface of dissipated energy, when
one of the points of contact D falls within the triangle formed by
the other three A, B, C. This surface includes the triangle ABC
in the quadruple tangent plane, portions of the three sheets of the
primitive surface which touch the triangle at its vertices, EAF, GBH,
ICK, and portions of the three developable surfaces formed by a
tangent plane rolling upon each pair of these sheets. These develop-
able surfaces are represented in the figure by ruled surfaces, the lines
indicating the direction of their rectilinear elements. A point within
the triangle ABC represents a mass of which the matter is divided,
in general, between three or four different phases, in a manner not
entirely determined by the position of a point. (The quantities of
matter in these phases are such that if placed at the corresponding
points, A, B, C, D, their center of gravity would be at the point
representing the total mass.) Such a mass, if exposed to constant
temperature and pressure, would be in neutral equilibrium. A
point in the developable surfaces represents a mass of which the
matter is divided between two coexisting phases, which are repre-
sented by the extremities of the line in the figure passing through
that point. A point in the primitive surface represents of course a
homogeneous mass.
To determine the effect of a change of temperature without change
of pressure upon the general features of the surface of dissipated
energy, we must know whether heat is absorbed or yielded by a
mass in passing from the phase represented by the point D in the
primitive surface to the composite state consisting of the phases A,
B, and C which is represented by the same point. If the first is the
case, an increase of temperature will cause the sheet (D) (i.e., the
sheet of the primitive surface to which the point D belongs) to
separate from the plane tangent to the three other sheets, so as to be
situated entirely above it, and a decrease of temperature, will cause
ja part of the sheet (D) to protrude through the plane tangent to
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
123
the other sheets. These effects will be produced by the opposite
changes of temperature, when heat is yielded by a mass passing
from the homogeneous to the composite state above mentioned.
In like manner, to determine the effect of a variation of pressure
without change of temperature, we must know whether the volume
for the homogeneous phase represented by D is greater or less than
the volume of the same matter divided between the phases A, B, and
0. If the homogeneous phase has the greater volume, an increase of
pressure will cause the sheet (D) to separate from the plane tangent to
the other sheets, and a diminution of pressure will cause a part of the
sheet (D) to protrude below that tangent plane. And these effects
will be produced by the opposite changes of pressure, if the homo-
geneous phase has the less volume. All this appears from precisely
Fig. 2.
Fig. 3.
the same considerations which were used in the analogous case for
two component substances.
Now when the sheet (D) rises above the plane tangent to the other
sheets, the general features of the surface of dissipated energy are
not altered, except by the disappearance of the point D. But when
the sheet (D) protrudes below the plane tangent to the other sheets,
the surface of dissipated energy will take the form indicated in figure 3.
It will include portions of the four sheets of the primitive surface,
portions of the six developable surfaces formed by a double tangent
plane rolling upon these sheets taken two by two, and portions of
three triple tangent planes for these sheets taken by threes, the sheet
(D) being always one of the three.
But when the points of contact with the quadruple tangent plane
which represent the four coexistent phases can be joined so as to
124 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
form a quadrilateral ABCD (fig. 4) without re-entrant angles, the
surface of dissipated energy will include this plane quadrilateral,
portions of the four sheets of the primitive surface which are tangent
to it, and portions of the four developable surfaces formed by double
tangent planes rolling upon the four pairs of these sheets which
correspond to the four sides of the quadrilateral. To determine the
general effect of a variation of temperature upon the surface of dis-
sipated energy, let us consider the composite states represented by the
point I at the intersection of the diagonals of the quadrilateral. Among
these states (which all relate to the same kind and quantity of matter)
there is one which is composed of the phases A and C, and another
which is composed of the phases B and D. Now if the entropy of
the first of these states is greater than that of the second (i.e., if
heat is given out by a body in passing from the first to the second
Fig. 4. Fig. 5.
state at constant temperature arid pressure), which we may suppose
without loss of generality, an elevation of temperature while the
pressure remains constant will cause the triple tangent planes to
(B), (D), and (A), and to (B), (D), and (C), to rise above the
triple tangent planes to (A), (C), and (B), and to (A), (C), and
(D), in the vicinity of the point I. The surface of dissipated
energy will therefore take the form indicated in figure 5, in which
there are two plane triangles and five developable surfaces besides
portions of the four primitive sheets. A diminution of temperature
will give a different but entirely analogous form to the surface of
dissipated energy. The quadrilateral ABCD will in this case break
into two triangles along the diameter BD. The effects produced by
variation of the pressure while the temperature remains constant will
of course be similar to those described. By considering the difference
of volume instead of the difference of entropy of the two states
represented by the point I in the quadruple tangent plane, we may
distinguish between the effects of increase and diminution of pressure.
It should be observed that the points of contact of the quadruple
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 125
tangent plane with the primitive surface may be at isolated points or
curves belonging to the latter. So also, in the case of two component
substances, the points of contact of the triple tangent line may be at
isolated points belonging to the primitive curve. Such cases need
not be separately treated, as the necessary modifications in the pre-
ceding statements, when applied to such cases, are quite evident.
And in the remaining discussion of this geometrical method, it will
generally be left to the reader to make the necessary limitations or
modifications in analogous cases.
The necessary condition in regard to simultaneous variations of
temperature and pressure, in order that four coexistent phases of
three components, or three coexistent phases of two components, shall
remain possible, has already been deduced by purely analytical pro-
cesses. (See equation (129).)
We will next consider the case of two coexistent phases of identi-
cal composition, and first, when the number of components is two.
The coexistent phases, if each is variable in composition, will be
represented by the point of contact of two curves. One of the curves
will in general lie above the other except at the point of contact;
therefore, when the temperature and pressure remain constant, one
phase cannot be varied in composition without becoming unstable,
while the other phase will be stable if the proportion of either
component is increased. By varying the temperature or pressure, we
may cause the upper curve to protrude below the other, or to rise
(relatively) entirely above it. (By comparing the volumes or the
entropies of the two coexistent phases, we may easily determine
which result would be produced by an increase of temperature or
of pressure.) Hence, the temperatures and pressures for which two
coexistent phases have the same composition form the limit to the
temperatures and pressures for which such coexistent phases are
possible. It will be observed that as we pass
this limit of temperature and pressure, the pair
of coexistent phases does not simply become
unstable, like pairs and triads of coexistent
phases which we have considered before, but
there ceases to be any such pair of coexistent
phases. The same result has already been p. .
obtained analytically on page 99. But on
that side of the limit on which the coexistent phases are possible,
there will be two pairs of coexistent phases for the same values
of t and p, as seen in figure 6. If the curve AA' represents vapor,
and the curve BB' liquid, a liquid (represented by) B may exist
in contact with a vapor A, and (at the same temperature and
pressure) a liquid B' in contact with a vapor A'. If we compare
126 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
these phases in respect to their composition, we see that in one case
the vapor is richer than the liquid in a certain component, and in the
other case poorer. Therefore, if these liquids are made to boil, the
effect on their composition will be opposite. If the boiling is con-
tinued under constant pressure, the temperature will rise as the liquids
approach each other in composition, and the curve BB' will rise
relatively to the curve AA', until the curves are tangent to each other,
when the two liquids become identical in nature, as also the vapors
which they yield. In composition, and in the value of f per unit of
mass, the vapor will then agree with the liquid. But if the curve
BB' (which has the greater curvature) represents vapor, and AA'
represents liquid, the effect of boiling will make the liquids A and
A' differ more in composition. In this case, the relations indicated
in the figure will hold for a temperature higher than that for which
(with the same pressure) the curves are tangent to one another.
When two coexistent phases of three component substances have
the same composition, they are represented by the point of contact of
two sheets of the primitive surface. If these sheets do not intersect
at the point of contact, the case is very similar to that which we have
just considered. The upper sheet except at the point of contact
represents unstable phases. If the temperature or pressure are so
varied that a part of the upper sheet protrudes through the lower,
the points of contact of a double tangent plane rolling upon the
two sheets will describe a closed curve on each, and the surface
of dissipated energy will include a portion of each sheet of the
primitive surface united by a ring-shaped developable surface.
If the sheet having the greater curvatures represents liquid,' and
the other sheet vapor, the boiling temperature for any given pressure
will be a maximum, and the pressure of saturated vapor for any
given temperature will be a minimum, when the coexistent liquid
and vapor have the same composition.
But if the two sheets, constructed for the temperature and pressure
of the coexistent phases which have the same composition, intersect
at the point of contact, the whole primitive
surface as seen from below will in general
present four re-entrant furrows, radiating
from the point of contact, for each of which
a developable surface may be formed by a
rolling double tangent plane. The different
parts of the surface of dissipated energy in
the vicinity of the point of contact are
represented in figure 7. ATB, ETF are
parts of one sheet of the primitive surface, and CTD, GTH are parts
of the other. These are united by the developable surfaces ETC,
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 127
DTE, FTG, HTA. Now we may make either sheet of the primitive
surface sink relatively to the other by the proper variation of
temperature or pressure. If the sheet to which ATB, ETF belong is
that which sinks relatively, these parts of the surface of dissipated
energy will be merged in one, as well as the developable surfaces ETC,
DTE, and also FTG, HTA. (The lines CTD, BTE, ATF, HTG will
separate from one another at T, each forming a continuous curve.)
But if the sheet of the primitive surface which sinks relatively is
that to which CTD and GTH belong, then these parts will be merged
in one in the surface of dissipated energy, as will be the developable
surfaces ETC, ATH, and also DTE, FTG.
It is evident that this is not a case of maximum or minimum tem-
perature for coexistent phases under constant pressure, or of maximum
or minimum pressure for coexistent phases at constant temperature.
Another case of interest is when the composition of one of three
coexistent phases is such as can be produced by combining the other
two. In this case, the primitive surface must touch the same plane
in three points in the same straight line. Let us distinguish the parts
of the primitive surface to which these points belong as the sheets (A),
(B), and (C), (C) denoting that which is intermediate in position.
The sheet (C) is evidently tangent to the developable surface formed
upon (A) and (B). It may or it may not intersect it at the point of
contact. If it does not, it must lie above the developable surface
(unless it represents states which are unstable in regard to continuous
changes), and the surface of dissipated energy will include parts of
the primitive sheets (A) and (B), the developable surface joining
them, and the single point of the sheet (C) in which it meets this
developable surface. Now, if the temperature or pressure is varied
so as to make the sheet (C) rise
above the developable surface
formed on the sheets (A) and (B),
the surface of dissipated energy
will be altered in its general
features only by the removal of
the single point of the sheet (C).
But if the temperature or pressure
is altered so as to make a part Flgl
of the sheet (C) protrude through the developable surface formed
on (A) and (B), the surface of dissipated energy will have the form
indicated in figure 8. It will include two plane triangles ABC and
A'B'C', a part of each of the sheets (A) and (B), represented in the
figure by the spaces on the left of the line aAAV and on the right of
the line bBB'b', a small part CC' of the sheet (C), and developable
surfaces formed upon these sheets taken by pairs ACC'A', BCC'B',
128 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
aABb, a'A'B'b', the last two being different portions of the same
developable surface.
But if, when the primitive surface is constructed for such a tem-
perature and pressure that it has three points of contact with the same
plane in the same straight line, the sheet (C) (which has the middle
position) at its point of contact with the triple tangent plane intersects
the developable surface formed upon the other sheets (A) and (B), the
surface of dissipated energy will not include this developable surface,
but will consist of portions of the three primitive sheets with two
developable surfaces formed on (A) and (C) and on (B) and (C). These
developable surfaces meet one another at the point of contact of (C)
with the triple tangent plane, dividing the portion of this sheet which
belongs to the surface of dissipated energy into two parts. If now
the temperature or pressure are varied so as to make the sheet (C)
sink relatively to the developable surface formed on (A) and (B), the
only alteration in the general features of the surface of dissipated
energy will be that the developable
surfaces formed on (A) and (C) and
on (B) and (C) will separate from
one another, and the two parts of
the sheet (C) will be merged in
one. But a contrary variation of
temperature or pressure will give a
surface of dissipated energy such
as is represented in figure (9), con-
taining two plane triangles ABC,
A'B'C' belonging to triple tangent planes, a portion of the shee't (A)
on the left of the line a AAV, a portion of the sheet (B) on the right of
the line bBB'b', two separate portions cCy and c'C'y' of the sheet (C),
two separate portions aACc and a'A'C'c' of the developable surface
formed on (A) and (C), two separate portions bBCy and b'B'C'y'
of the developable surface formed on (B) and (C), and the portion
A'ABB' of the developable surface formed on (A) and (B).
From these geometrical relations it appears that (in general) the
temperature of three coexistent phases is a maximum or minimum
for constant pressure, and the pressure of three coexistent phases a
maximum or minimum for constant temperature, when the com-
position of the three coexistent phases is such that one can be
formed by combining the other two. This result has been obtained
analytically on page 99.
The preceding examples are amply sufficient to illustrate the use of
the m-f surfaces and curves. The physical properties indicated by the
nature of the surface of dissipated energy have been only occasionally
mentioned, as they are often far more distinctly indicated by the
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 129
diagrams than they could be in words. It will be observed that a
knowledge of the lines which divide the various different portions of
the surface of dissipated energy and of the direction of the rectilinear
elements of the developable surfaces, as projected upon the X- Y plane,
without a knowledge of the form of the m-f surface in space, is
sufficient for the determination (in respect to the quantity and com-
position of the resulting masses) of the combinations and separations
of the substances, and of the changes in their states of aggregation,
which take place when the substances are exposed to the temperature
and pressure to which the projected lines relate, except so far as such
transformations are prevented by passive resistances to change.
Critical Phases.
It has been ascertained by experiment that the variations of two
coexistent states of the same substance are in some cases limited in
one direction by a terminal state at which the distinction of the
coexistent states vanishes.* This state has been called the critical
state. Analogous properties may doubtless be exhibited by com-
pounds of variable composition without change of temperature or
pressure. For if, at any given temperature and pressure, two liquids
are capable of forming a stable mixture in any ratio m^ : m2 less than
a, and in any greater than b, a and b being the values of that ratio
for two coexistent phases, while either can form a stable mixture with
a third liquid in all proportions, and any small quantities of the first
and second can unite at once with a great quantity of the third to
form a stable mixture, it may easily be seen that two coexistent
mixtures of the three liquids may be varied in composition, the
temperature and pressure remaining the same, from initial phases
in each of which the quantity of the third liquid is nothing, to a
terminal phase in which the distinction of the two phases vanishes.
In general, we may define a critical phase as one at which the
distinction between coexistent phases vanishes. We may suppose
the coexistent phases to be stable in respect to continuous changes,
for although relations in some respects analogous might be imagined
to hold true in regard to phases which are unstable in respect to
continuous changes, the discussion of such cases would be devoid
of interest. But if the coexistent phases and the critical phase are
unstable only in respect to the possible formation of phases entirely
different from the critical and adjacent phases, the liability to such
changes will in no respect affect the relations between the critical and
adjacent phases, and need not be considered in a theoretical discussion
*See Dr. Andrews "On the continuity of the gaseous and liquid states of matter."
Phil Trans., vol. 159, p. 575.
G. I. I
130 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
of these relations, although it may prevent an experimental realization
of the phases considered. For the sake of brevity, in the following
discussion, phases in the vicinity of the critical phase will generally be
called stable, if they are unstable only in respect to the formation of
phases entirely different from any in the vicinity of the critical phase.
Let us first consider the number of independent variations of which
a critical phase (while remaining such) is capable. If we denote
by n the number of independently variable components, a pair of
coexistent phases will be capable of n independent variations, which
may be expressed by the variations of n of the quantities t, p, /x1}
fjL2,...fin. If we limit these variations by giving to n—l of the
quantities the constant values which they have for a certain critical
phase, we obtain a linear* series of pairs of coexistent phases ter-
minated by the critical phase. If we now vary infinitesimally the
values of these n — l quantities, we shall have for the new set of
values considered constant a new linear series of pairs of coexistent
phases. Now for every pair of phases in the first series, there must be
pairs of phases in the second series differing infinitely little from the
pair in the first, and vice versa, therefore the second series of coexistent
phases must be terminated by a critical phase which differs, but differs
infinitely little, from the first. We see, therefore, that if we vary
arbitrarily the values of any n — 1 of the quantities, t, p, JUL^ ju.2, . . . /zn,
as determined by a critical phase, we obtain one and only one critical
phase for each set of varied values; i.e., a critical phase is capable
of n — 1 independent variations.
The quantities t, p, JJLV /m.2, . . . JULU have the same values in two
coexistent phases, but the ratios of the quantities r], v} mv mz, . . . mn
are in general different in the two phases. Or, if for convenience we
compare equal volumes of the two phases (which involves no loss of
generality), the quantities q, mv m2, ... mn will in general have dif-
ferent values in two coexistent phases. Applying this to coexistent
phases indefinitely near to a critical phase, we see that in the
immediate vicinity of a critical phase, if the values of n of the
quantities t, p, filt yM2, ... /xn are regarded as constant (as well as v),
the variations of either of the others will be infinitely small compared
with the variations of the quantities 77, mv m2, . . . mn. This condition,
which we may write in the form
=°- (200>
Vt w,".Mn-i
characterizes, as we have seen on page 114, the limits which divide
stable from unstable phases in respect to continuous changes.
In fact, if we give to the quantities t, JULV JULZ, ... fin-1 constant values
* This term is used to characterize a series having a single degree of extension.
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 131
/yvi
determined by a pair of coexistent phases, and to - - a series of
values increasing from the less to the greater of the values which it
has in these coexistent phases, we determine a linear series of phases
connecting the coexistent phases, in some part of which juLn — since it
has the same value in the two coexistent phases, but not a uniform
value throughout the series (for if it had, which is theoretically im-
probable, all these phases would be coexistent) — must be a decreasing
vn
function of — , or of mn, if v also is supposed constant. Therefore,
the series must contain phases which are unstable in respect to con-
tinuous changes. (See page 111.) And as such a pair of coexistent
phases may be taken indefinitely near to any critical phase, the
unstable phases (with respect to continuous changes) must approach
indefinitely near to this phase.
Critical phases have similar properties with reference to stability
as determined with regard to discontinuous changes. For as every"
stable phase which has a coexistent phase lies upon the limit which
separates stable from unstable phases, the same must be true of any
stable critical phase. (The same may be said of critical phases which
are unstable in regard to discontinuous changes, if we leave out of
account the liability to the particular kind of discontinuous change
in respect to which the critical phase is unstable.)
The linear series of phases determined by giving to n of the
quantities t, p, fa, fa, ... /u.n the constant values which they have in
any pair of coexistent phases consists of unstable phases in the part
between the coexistent phases, but in the part beyond these phases in
either direction it consists of stable phases. Hence, if a critical phase
is varied in such a manner that n of the quantities t, p, fa, fa, ... JULU
remain constant, it will remain stable in respect both to continuous
and to discontinuous changes. Therefore /mn is an increasing function
of mn when t, v, fa, fa, ... JULU-I have constant values determined by
any critical phase. But as equation (200) holds true at the critical
phase, the following conditions must also hold true at that phase : —
„ =0, (201)
t, V, Ml> — Mn-1
(202)
Mn-l
If the sign of equality holds in the last condition, additional conditions,
concerning the differential coefficients of higher orders, must be satisfied.
Equations (200) and (201) may in general be called the equations
of critical phases. It is evident that there are only two independent
equations of this character, as a critical phase is capable of n — 1 inde-
pendent variations.
132 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
We are not, however, absolutely certain that equation (200) will
always be satisfied by a critical phase. For it is possible that the
denominator in the fraction may vanish as well as the numerator for
an infinitesimal change of phase in which the quantities indicated
are constant. In such a case, we may suppose the subscript n to
refer to some different component substance, or use another differ-
ential coefficient of the same general form (such as are described on
page 114 as characterizing the limits of stability in respect to con-
tinuous changes), making the corresponding changes in (201) and
(202). We may be certain that some of the formulae thus formed
will not fail. But for a perfectly rigorous method there is an
advantage in the use of T], v, fml, m2,...mn as independent variables.
The condition that the phase may be varied without altering any of
the quantities t, fa, /i2, ... jun will then be expressed by the equation
7? —0 ^20^
J-^n+i — u> ^ziuo;
in which Rn+l denotes the same determinant as on page 111. To
obtain the second equation characteristic of critical phases, we observe
that as a phase which is critical cannot become unstable when varied
so that n of the quantities t, p, fa, fa, ... //n remain constant, the
differential of Rn+i for constant volume, viz.,
dR dR dR
— T^-dn-\ — T^—dm, ... -\ — ,-^cZmn, (204)
rt vi fi IVY) *• dfyv) '
(A//I \Jjlli/-i U/ 1 1 (/ft
cannot become negative when n of the equations (172) are satisfied.
Neither can it have a positive value, for then its value might become
negative by a change of sign of dr\, dm^ etc. Therefore the expression
(204) has the value zero, if n of the equations (172) are ' satisfied.
This may be expressed by an equation
S=0, (205)
in which S denotes a determinant in which the constituents are the
same as in Rn+i, except in a single horizontal line, in which the
differential coefficients in (204) are to be substituted. In whatever
line this substitution is made, the equation (205), as well as (203),
will hold true of every critical phase without exception.
If we choose t, p, m^, m2,...mn as independent variables, and
write U for the determinant
«p?
dX
(206)
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 133
and V for the determinant formed from this by substituting for the
constituents in any horizontal line the expressions
dU_ dU_ dU
dm^ dm2' c£ran_i'
the equations of critical phases will be
tf=0, F=0. (208)
It results immediately from the definition of a critical phase, that
an infinitesimal change in the condition of a mass in such a phase
may cause the mass, if it remains in a state of dissipated energy (i.e.,
in a state in which the dissipation of energy, by internal processes is
complete), to cease to be homogeneous. In this respect a critical phase
resembles any phase which has a coexistent phase, but differs from
such phases in that the two parts into which the mass divides when
it ceases to be homogeneous differ infinitely little from each other and
from the original phase, and that neither of these parts is in general"
infinitely small. If we consider a change in the mass to be determined
by the values of drj, dv, d^, dmz,...dmn, it is evident that the
change in question will cause the mass to cease to be homogeneous
whenever the expression
has a negative value. For if the mass should remain homogeneous,
it would become unstable, as Mn+i would become negative. Hence, in
general, any change thus determined, or its reverse (determined by
giving to drj, dv, dm1} dm2, ... dmn the same values taken negatively)
will cause the mass to cease to be homogeneous. The condition which
must be satisfied with reference to drj, dv, dml} dm2, ... dmn, in order
that neither the change indicated, nor the reverse, shall destroy the
homogeneity of the mass, is expressed by equating the above expres-
sion to zero.
But if we consider the change in the state of the mass (supposed to
remain in a state of dissipated energy) to be determined by arbitrary
values of n + l of the differentials dt, dp, djuv d/ui2, ... dfin, the case
will be entirely different. For, if the mass ceases to be homogeneous,
it will consist of two coexistent phases, and as applied to these, only n
of the quantities t, p, fjLl} jULz,...ju.n will be independent. Therefore,
for arbitrary variations of n+l of these quantities, the mass must in
general remain homogeneous.
But if, instead of supposing the mass to remain in a state of dissi-
pated energy, we suppose that it remains homogeneous, it may easily
be shown that to certain values of n+l of the above differentials
134 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
there will correspond three different phases, of which one is stable
with respect both to continuous and to discontinuous changes, another
is stable with respect to the former and unstable with respect to the
latter, and the third is unstable with respect to both.
In general, however, if n of the quantities p, t, //j, //2, ... /zn, or n
arbitrary functions of these quantities, have the same constant values
as at a critical phase, the linear series of phases thus determined will
be stable, in the vicinity of the critical phase. But if less than n of
these quantities or functions of the same together with certain of the
quantities r\, v, ml} m2,...mn, or arbitrary functions of the latter
quantities, have the same values as at a critical phase, so as to
determine a linear series of phases, the differential of Rn+i in such a
series of phases will not in general vanish at the critical phase, so that
in general a part of the series will be unstable.
We may illustrate these relations by considering separately the cases
in which n = 1 and n = 2. If a mass of invariable composition is in a
critical state, we may keep its volume constant, and destroy its homo-
geneity by changing its entropy (i.e., by adding or subtracting heat —
probably the latter), or we may keep its entropy constant and destroy
its homogeneity by changing its volume ; but if we keep its pressure
constant we cannot destroy its homogeneity by any thermal action,
nor if we keep its temperature constant can we destroy its homo-
geneity by any mechanical action.
When a mass having two independently variable components is in
a critical phase, and either its volume or its pressure is maintained
constant, its homogeneity may be destroyed by a change of entropy
or temperature. Or, if either its entropy or its temperature 'is main-
tained constant, its homogeneity may be destroyed by a change of
volume or pressure. In both these cases it is supposed that the
quantities of the components remain unchanged. But if we suppose
both the temperature and the pressure to be maintained constant, the
mass will remain homogeneous, however the proportion of the com-
ponents be changed. Or, if a mass consists of two coexistent phases,
one of which is a critical phase having two independently variable
components, and either the temperature or the pressure of the mass is
maintained constant, it will not be possible by mechanical or thermal
means, or by changing the quantities of the components, to cause the
critical phase to change into a pair of coexistent phases, so as to give
three coexistent phases in the whole mass. The statements of this
paragraph and of the preceding have reference only to infinitesimal
changes.*
* A brief abstract (which came to the author's notice after the above was in type) of a
memoir by M. Duclaux, " Sur la separation des liquides melanges, etc." will be found in
Comptes Rendus, vol. Ixxxi. (1875), p. 815.
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 135
On the Values of the Potentials when the Quantity of one of
the Components is very small.
If we apply equation (97) to a homogeneous mass having two
independently variable components S1 and Sz, and make t, p, and ml
constant, we obtain
=0. (210)
P> ,Bl fl»y i, p, mi
Therefore, for ra2 = 0, either
= 0, (211)
or Kl =00. (212)
Pi
Now, whatever may be the composition of the mass considered, we
may always so choose the substance /S^ that the mass shall consist
solely of that substance, and in respect to any other variable com-
ponent S2, we shall have ra2 = 0. But equation (212) cannot hold true
in general as thus applied. For it may easily be shown (as has been
done with regard to the potential on pages 92, 93) that the value of
a differential coefficient like that in (212) for any given mass, when
the substance S2 (to which ra2 and //2 relate) is determined, is inde-
pendent of the particular substance which we may regard as the other
component of the mass ; so that, if equation (212) holds true when the
substance denoted by Sl has been so chosen that m2 = 0, it must hold
true without such a restriction, which cannot generally be the case.
In fact, it is easy to prove directly that equation (211) will hold
true of any phase which is stable in regard to continuous changes and
in which m2 = 0, if m2 is capable of negative as well as positive values.
For by (171), in any phase having that kind of stability, fa is an
increasing function of rax when t, p, and m2 are regarded as constant.
Hence, /zx will have its greatest value when the mass consists wholly
of Slt i.e., when m2 = 0. Therefore, if m2 is capable of negative as well
as positive values, equation (211) must hold true for m2 = 0. (This
appears also from the geometrical representation of potentials in the
-m-f curve. See page 119.)
But if m2 is capable only of positive values, we can only conclude
from the preceding considerations that the value of the differential
coefficient in (211) cannot be positive. Nor, if we consider the
physical significance of this case, viz., that an increase of m2 denotes
an addition to the mass in question of a substance not before
contained in it, does any reason appear for supposing that this
differential coefficient has generally the value zero. To fix our
136 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
ideas, let us suppose that Sl denotes water, and 82 a salt (either
anhydrous or any particular hydrate). The addition of the salt to
water, previously in a state capable of equilibrium with vapor
or with ice, will destroy the possibility of such equilibrium at the
same temperature and pressure. The liquid will dissolve the ice, or
condense the vapor, which is brought in contact with it under
such circumstances, which shows that fa (the potential for water
in the liquid mass) is diminished by the addition of the salt, when
the temperature and pressure are maintained constant. Now there
seems to be no a priori reason for supposing that the ratio of this
diminution of the potential for water to the quantity of the salt
which is added vanishes with this quantity. We should rather
expect that, for small quantities of the salt, an effect of this kind
would be proportional to its cause, i.e., that the differential coefficient
in (211) would have a finite negative value for an infinitesimal value of
m2. That this is the case with respect to numerous watery solutions
of salts is distinctly indicated by the experiments of Wiillner * on the
tension of the vapor yielded by such solutions, and of Riidorff t on the
temperature at which ice is formed in them ; and unless we have
experimental evidence that cases are numerous in which the contrary
is true, it seems not unreasonable to assume, as a general law, that
when m2 has the value zero and is incapable of negative values, the
differential coefficient in (211) will have a finite negative value, and
that equation (212) will therefore hold true. But this case must be
carefully distinguished from that in which m2 is capable of negative
values, which also may be illustrated by a solution of a salt in water.
For this purpose let Sl denote a hydrate of the salt which 'can be
crystallized, and let $2 denote water, and let us consider a liquid con-
sisting entirely of St and of such temperature and pressure as to be in
equilibrium with crystals of Sr In such a liquid, an increase or a
diminution of the quantity of water would alike cause crystals of S1
to dissolve, which requires that the differential coefficient in (211)
shall vanish at the particular phase of the liquid for which m2 = 0.
Let us return to the case in which m2 is incapable of negative
values, and examine, without other restriction in regard to the sub-
Tfi
stances denoted by 8l and $2, the relation between /z2 and — - for any
ii 6-1
constant temperature and pressure and for such small values of •
l/C'i
that the differential coefficient in (211) may be regarded as having the
same constant value as when m2 = 0, the values of t, p, and m^ being
unchanged. If we denote this value of the differential coefficient by
*Pogg. Ann., vol. ciii. (1858), p. 529; vol. cv. (1858), p. 85; vol. ex. (1860), p. 564.
i-Pogg. Ann., vol. cxiv. (1861), p. 63.
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 137
A
-, the value of A will be positive, and will be independent of mr
mi m
Then for small values of - ? we have by (210), approximately,
7/C/l
(213)
If we write the integral of this equation in the form
(215)
£ like A will have a positive value depending only upon the tem-
perature and pressure. As this equation is to be applied only to cases
in which the value of m2 is very small compared with m1? we may
regard — - as constant, when temperature and pressure are constant,
and write (7m«
*> (216)
C denoting a positive quantity, dependent only upon the temperature
and pressure.
We have so far considered the composition of the body as varying
only in regard to the proportion of two components. But the argu-
ment will be in no respect invalidated, if we suppose the composition
of the body to be capable of other variations. In this case, the
quantities A and C will be functions not only of the temperature and
pressure but also of the quantities which express the composition of
the substance of which together with $2 the body is composed. If
the quantities of any of the components besides $2 are very small
(relatively to the quantities of others), it seems reasonable to assume
that the value of /z2, and therefore the values of A and (7, will be
nearly the same as if these components were absent.
Hence, if the independently variable components of any body are
Sa, ...Sy, and Sh,...Sk, the quantities of the latter being very small
as compared with the quantities of the former, and are incapable of
negative values, we may express approximately the values of the
potentials for Sh,...Sk by equations (subject of course to the uncer-
tainties of the assumptions which have been made) of the form
, (217)
, (218)
in which Ah, Ch, ... Ak, Ck denote functions of the temperature, the
pressure, and the ratios of the quantities ma, ... ma.
138 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
We shall see hereafter, when we come to consider the properties of
gases, that these equations may be verified experimentally in a very
large class of cases, so that we have considerable reason for believing
that they express a general law in regard to the limiting values of
potentials.*
On Certain Points relating to the Molecular Constitution
of Bodies.
It not unfrequently occurs that the number of proximate com-
ponents which it is necessary to recognize as independently variable
in a body exceeds the number of components which would be
sufficient to express its ultimate composition. Such is the case, for
example, as has been remarked on page 63, in regard to a mixture
at ordinary temperatures of vapor of water and free hydrogen and
oxygen. This case is explained by the existence of three sorts of
molecules in the gaseous mass, viz., molecules of hydrogen, of
oxygen, and of hydrogen and oxygen combined. In other cases,
which are essentially the same in principle, we suppose a greater
number of different sorts of molecules, which differ in composition,
and the relations between these may be more complicated. Other
cases are explained by molecules which differ in the quantity of
matter which they contain, but not in the kind of matter, nor in
the proportion of the different kinds. In still other cases, there
appear to be different sorts of molecules, which differ neither in the
kind nor in the quantity of matter which they contain, but only
in the manner in which they are constituted. What is essential in
the cases referred to is that a certain number of some sort or sorts of
molecules shall be equivalent to a certain number of some other sort
or sorts in respect to the kinds and quantities of matter which they
collectively contain, and yet the former shall never be transformed into
the latter within the body considered, nor the latter into the former,
however the proportion of the numbers of the different sorts of
molecules may be varied, or the composition of the body in other
respects, or its thermodynamic state as represented by temperature
and pressure or any other two suitable variables, provided, it may
be, that these variations do not exceed certain limits. Thus, in the
* The reader will not fail to remark that, if we could assume the universality of this
law, the statement of the conditions necessary for equilibrium between different
masses in contact would be much simplified. For, as the potential for a substance
which is only a possible component (see page 64) would always have the value - oo ,
the case could not occur that the potential for any substance would have a greater
value in a mass in which that substance is only a possible component, than in another
mass in which it is an actual component ; and the conditions (22) and (51) might be
expressed with the sign of equality without exception for the case of possible
components.
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 139
example given above, the temperature must not be raised beyond
a certain limit, or molecules of hydrogen and of oxygen may be
transformed into molecules of water.
The differences in bodies resulting from such differences in the
constitution of their molecules are capable of continuous variation,
in bodies containing the same matter and in the same thermodynamic
state as determined, for example, by pressure and temperature, as the
numbers of the molecules of the different sorts are varied. These
differences are thus distinguished from those which depend upon the
manner in which the molecules are combined to form sensible masses.
The latter do not cause an increase in the number of variables in the
fundamental equation ; but they may be the cause of different values
of which the function is sometimes capable for one set of values of
the independent variables, as, for example, when we have several
different values of f for the same values of t, p, mv m2, ... mn, one
perhaps being for a gaseous body, one for a liquid, one for an amor-
phous solid, and others for different kinds of crystals, and all being
invariable for constant values of the above mentioned independent
variables.
But it must be observed that when the differences in the constitu-
tion of the molecules are entirely determined by the quantities of
the different kinds of matter in a body with the two variables which
express its thermodynamic state, these differences will not involve
any increase in the number of variables in the fundamental equation.
For example, if we should raise the temperature of the mixture of
vapor of water and free hydrogen and oxygen, which we have just
considered, to a point at which the numbers of the different sorts of
molecules are entirely determined by the temperature and pressure
and the total quantities of hydrogen and of oxygen which are present,
the fundamental equation of such a mass would involve but four
independent variables, which might be the four quantities just
mentioned. The fact of a certain part of the matter present existing
in the form of vapor of water would, of course, be one of the facts
which determine the nature of the relation between f and the
independent variables, which is expressed by the fundamental
equation.
But in the case first considered, in which the quantities of the
different sorts of molecules are not determined by the temperature
and pressure and the quantities of the different kinds of matter in the
body as determined by its ultimate analysis, the components of which
the quantities or the potentials appear in the fundamental equation
must be those which are determined by the proximate analysis of the
body, so that the variations in their quantities, with two variations
relating to the thermodynamic state of the body, shall include all
140 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
the variations of which the body is capable.* Such cases present
no especial difficulty; there is indeed nothing in the physical and
chemical properties of such bodies, so far as a certain range of
experiments is concerned, which is different from what might be,
if the proximate components were incapable of farther reduction or
transformation. Yet among the various phases of the kinds of matter
concerned, represented by the different sets of values of the variables
which satisfy the fundamental equation, there is a certain class which
merits especial attention. These are the phases for which the entropy
has a maximum value for the same matter, as determined by the
ultimate analysis of the body, with the same energy and volume.
To fix our ideas let us call the proximate components 8lt ... Sn, and
the ultimate components Sat...Sh; and let mv ...mn denote the
quantities of the former, and ma, ... mh) the quantities of the latter.
It is evident that ma,...mh are homogeneous functions of the first
degree of mlt . . . mn ; and that the relations between the substances
Sv ... Sn might be expressed by homogeneous equations of the first
degree between the units of these substances, equal in number to
the difference of the numbers of the proximate and of the ultimate
components. The phases in question are those for which r\ is a
maximum for constant values of e, v, ma, ... tnh; or, as they may also
be described, those for which e is a minimum for constant values
of 77, v, ma, ...?%; or for which f is a minimum for constant values
of t, p, ma,...mfe. The phases which satisfy this condition may be
readily determined when the fundamental equation (which will
contain the quantities mv ...mn or fjLv ... fjin,) is known. Indeed it
is easy to see that we may express the conditions which determine
these phases by substituting yup . . . //„ for the letters denoting the
units of the corresponding substances in the equations which express
the equivalence in ultimate analysis between these units.
These phases may be called, with reference to the kind of change
which we are considering, phases of dissipated energy. That we
have used a similar term before, with reference to a different kind
of changes, yet in a sense entirely analogous, need not create
confusion.
It is characteristic of these phases that we cannot alter the values
of mlt . . . mn in any real mass in such a phase, while the volume of
the mass as well as its matter remain unchanged, without diminishing
the energy or increasing the entropy of some other system. Hence,
if the mass is large, its equilibrium can be but slightly disturbed
*The terms proximate or ultimate are not necessarily to be understood in an
absolute sense. All that is said here and in the following paragraphs will apply
to many cases in which components may conveniently be regarded as proximate or
ultimate, which are such only in a relative sense.
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 141
by the action of any small body, or by a single electric spark, or
by any cause which is not in some way proportioned to the effect
to be produced. But when the proportion of the proximate com-
ponents of a mass taken in connection with its temperature and
pressure is not such as to constitute a phase of dissipated energy,
it may be possible to cause great changes in the mass by the contact
of a very small body. Indeed it is possible that the changes produced
by such contact may only be limited by the attainment of a phase
of dissipated energy. Such a result will probably be produced in
a fluid mass by contact with another fluid which contains molecules
of all the kinds which occur in the first fluid (or at least all those
which contain the same kinds of matter which also occur in other
sorts of molecules), but which differs from the first fluid in that the
quantities of the various kinds of molecules are entirely determined
by the ultimate composition of the fluid and its temperature and
pressure. Or, to speak without reference to the molecular state of the
fluid, the result considered would doubtless be brought about by
contact with another fluid, which absorbs all the proximate com-
ponents of the first, Sv ... Sn (or all those between which there
exist relations of equivalence in respect to their ultimate analysis),
independently, and without passive resistances, but for which the
phase is completely determined by its temperature and pressure
and its ultimate composition (in respect at least to the particular
substances just mentioned). By the absorption of the substances
Sv... Sn independently and without passive resistances, it is meant
that when the absorbing body is in equilibrium with another contain-
ing these substances, it shall be possible by infinitesimal changes
in these bodies to produce the exchange of all these substances in
either direction and independently. An exception to the preceding
statement may of course be made for cases in which the result in
question is prevented by the occurrence of some other kinds of change;
in other words, it is assumed that the two bodies can remain in
contact preserving the properties which have been mentioned.
The term catalysis has been applied to such action as we are
considering. When a body has the property of reducing another,
without limitation with respect to the proportion of the two bodies,
to a phase of dissipated energy, in regard to a certain kind of
molecular change, it may be called a perfect catalytic agent with
respect to the second body and the kind of molecular change
considered.
It seems not improbable that in some cases in which molecular
changes take place slowly in homogeneous bodies, a mass of which
the temperature and pressure are maintained constant will be finally
brought to a state of equilibrium which is entirely determined by
142 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
its temperature and pressure and the quantities of its ultimate
components, while the various transitory states through which the
mass passes (which are evidently not completely defined by the
quantities just mentioned) may be completely defined by the quantities
of certain proximate components with the temperature and pressure,
and the matter of the mass may be brought by processes approxi-
mately reversible from permanent states to these various transitory
states. In such cases, we may form a fundamental equation with
reference to all possible phases, whether transitory or permanent;
and we may also form a fundamental equation of different import
and containing a smaller number of independent variables, which
has reference solely to the final phases of equilibrium. The latter
are the phases of dissipated energy (with reference to molecular
changes), and when the more general form of the fundamental
equation is known, it will be easy to derive from it the fundamental
equation for these permanent phases alone.
Now, as these relations, theoretically considered, are independent
of the rapidity of the molecular changes, the question naturally arises,
whether in cases in which we are not able to distinguish such
transitory phases, they may not still have a theoretical significance.
If so, the consideration of the subject from this point of view, may
assist us, in such cases, in discovering the form of the fundamental
equation with reference to the ultimate components, which is the
only equation required to express all the properties of the bodies
which are capable of experimental demonstration. Thus, when the
phase of a body is completely determined by the quantities 4of n
independently variable components, with the temperature and pres-
sure, and we have reason to suppose that the body is composed of
a greater number n' of proximate components, which are therefore
not independently variable (while the temperature and pressure
remain constant), it seems quite possible that the fundamental
equation of the body may be of the same form as the equation for
the phases of dissipated energy of analogous compounds of nf proxi-
mate and n ultimate components, in which the proximate components
are capable of independent variation (without variation of temperature
or pressure). And if such is found to be the case, the fact will be
of interest as affording an indication concerning the proximate con-
stitution of the body.
Such considerations seem to be especially applicable to the very
common case in which at certain temperatures and pressures, regarded
as constant, the quantities of certain proximate components of a
mass are capable of independent variations, and all the phases pro-
duced by these variations are permanent in their nature, while at
other temperatures and pressures, likewise regarded as constant, the
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 143
quantities of these proximate components are not capable of inde-
pendent variation, and the phase may be completely defined by the
quantities of the ultimate components with the temperature and
pressure. There may be, at certain intermediate temperatures and
pressures, a condition with respect to the independence of the
proximate components intermediate in character, in which the
quantities of the proximate components are independently variable
when we consider all phases, the essentially transitory as well as the
permanent, but in which these quantities are not independently
variable when we consider the permanent phases alone. Now we
have no reason to believe that the passing of a body in a state of
dissipated energy from one to another of the three conditions men-
tioned has any necessary connection with any discontinuous change
of state. Passing the limit which separates one of these states from
another will not therefore involve any discontinuous change in the
values of any of the quantities enumerated in (99)-(103) on page 88,
if mlt ra2, ... ran, //1? yu2,.../zn are understood as always relating to
the ultimate components of the body. Therefore, if we regard masses
in the different conditions mentioned above as having different
fundamental equations (which we may suppose to be of any one
of the five kinds described on page 88), these equations will agree
at the limits dividing these conditions not only in the values of
all the variables which appear in the equations, but also in all the
differential coefficients of the first order involving these variables.
We may illustrate these relations by supposing the values of t, p,
and f for a mass in which the quantities of the ultimate components
are constant to be represented by rectilinear coordinates. Where the
proximate composition of such a mass is not determined by t and p,
the value of f will not be determined by these variables, and the
points representing connected values of t, p, and f will form a solid.
This solid will be bounded in the direction opposite to that in which
f is measured, by a surface which represents the phases of dissipated
energy. In a part of the figure, all the phases thus represented may
be permanent, in another part only the phases in the bounding surface,
and in a third part there may be no such solid figure (for any phases
of which the existence is experimentally demonstrable), but only a
surface. This surface together with the bounding surfaces representing
phases of dissipated energy in the parts of the figure mentioned above
forms a continuous sheet, without discontinuity in regard to the
direction of its normal at the limits dividing the different parts of
the figure which have been mentioned. (There may, indeed, be
different sheets representing liquid and gaseous states, etc., but if we
limit our consideration to states of one of these sorts, the case will
be as has been stated.)
144 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
We shall hereafter, in the discussion of the fundamental equations
of gases, have an example of the derivation of the fundamental
equation for phases of dissipated energy (with respect to the mole-
cular changes on which the proximate composition of the body
depends) from the more general form of the fundamental equation.
The Conditions of Equilibrium for Heterogeneous Masses under
the Influence of Gravity.
Let us now seek the conditions of equilibrium for a mass of various
kinds of matter subject to the influence of gravity. It will be con-
venient to suppose the mass enclosed in an immovable envelop which
is impermeable to matter and to heat, and in other respects, except
in regard to gravity, to make the same suppositions as on page 62.
The energy of the mass will now consist of two parts, one of which
depends upon its intrinsic nature and state, and the other upon its
position in space. Let Dm denote an element of the mass, De the
intrinsic energy of this element, h its height above a fixed horizontal
plane, and g the force of gravity ; then the total energy of the mass
(when without sensible motions) will be expressed by the formula
fDe+fghDm, (219)
in which the integrations include all the elements of the mass ; and
the general condition of equilibrium will be
SfDe + Sfgh Dm ^ 0, (220)
the variations being subject to certain equations of condition. < These
must express that the entropy of the whole mass is constant, that
the surface bounding the whole mass is fixed, and that the total
quantity of each of the component substances is constant. We shall
suppose that there are no other equations of condition, and that
the independently variable components are the same throughout the
whole mass ; and we shall at first limit ourselves to the consideration
of the conditions of equilibrium with respect to the changes which
may be expressed by infinitesimal variations of the quantities which
define the initial state of the mass, without regarding the possibility
of the formation at any place of infinitesimal masses entirely different
from any initially existing in the same vicinity.
Let Dq, Dv, Dml,...Dmn denote the entropy of the element Dm,
its volume, and the quantities which it contains of the various com-
ponents. Then
Dm = Dml ... +Dmn, (221)
and SDm = SDml... +SDmn. (222)
Also, by equation (12),
(223)
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 145
By these equations the general condition of equilibrium may be
reduced to the form
ft SDn-fp SDv+ffr SDmt ... +//*„ SDmn
+fg ShDm +fgh 8Dml . . . +fgh SDmn > 0. (224)
Now it will be observed that the different equations of condition
affect different parts of this condition, so that we must have,
separately,
ftSDri^Q, if fSDri = 0; (225)
-fp SDv +fg ShDm ^ 0, (226)
if the bounding surface is unvaried ;
^Q, if /d-Dm^O;
(227)
n^Q, if fSDmn=0. ,
From (225) we may derive the condition of thermal equilibrium,
t = const. (228)
Condition (226) is evidently the ordinary mechanical condition of
equilibrium, and may be transformed by any of the usual methods.
We may, for example, apply the formula to such motions as might
take place longitudinally within an infinitely narrow tube, terminated
at both ends by the external surface of the mass, but otherwise
of indeterminate form. If we denote by m the mass, and by v the
volume, included in the part of the tube between one end and a
transverse section of variable position, the condition will take the form
-fp Sdv+fg Sh dm ^ 0, (229)
in which the integrations include the whole contents of the tube.
Since no motion is possible at the ends of the tube,
fp Sdv +JSv dp =fd(p Sv) = 0. (230)
Again, if we denote by y the density of the fluid,
fg Sh dm =fg ^Svydv =fgy Sv dh. (231)
By these equations condition (229) may be reduced to the form
fSv (dp +gy dh) ^ 0. (232)
Therefore, since Sv is arbitrary in value,
dp=-g-ydh, (233)
which will hold true at any point in the tube, the differentials being
taken with respect to the direction of the tube at that point. There-
fore, as the form of the tube is indeterminate, this equation must hold
true, without restriction, throughout the whole mass. It evidently
G.I. K
146 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
requires that the pressure shall be a function of the height alone,
and that the density shall be equal to the first derivative of this
function, divided by — g.
Conditions (227) contain all that is characteristic of chemical
equilibrium. To satisfy these conditions it is necessary and sufficient
that
= const.
fin-\-gh = const
.;
(234)
The expressions fiv ... jULn denote quantities which we have called
the potentials for the several components, and which are entirely
determined at any point in a mass by the nature and state of the
mass about that point. We may avoid all confusion between these
quantities and the potential of the force of gravity, if we distinguish
the former, when necessary, as intrinsic potentials. The relations
indicated by equations (234) may then be expressed as follows : —
When a fluid mass is in equilibrium under the influence of gravity,
and has the same independently variable components throughout, the
intrinsic potentials for the several components are constant in any
given level, and diminish uniformly as the height increases, the differ-
ence of the values of the intrinsic potential for any component at two
different levels being equal to the work done by the force of gravity
when a unit of matter falls from the higher to the lower level.
The conditions expressed by equations (228), (233), (234) are
necessary and sufficient for equilibrium, except with respec,t to the
possible formation of masses which are not approximately identical in
phase with any previously existing about the points where they may
be formed. The possibility of such formations at any point is evidently
independent of the action of gravity, and is determined entirely by
the phase or phases of the matter about that point. The conditions of
equilibrium in this respect have been discussed on pages 74-79.
But equations (228), (233), and (234) are not entirely independent.
For with respect to any mass in which there are no surfaces of dis-
continuity (i.e., surfaces where adjacent elements of mass have finite
differences of phase), one of these equations will be a consequence of
the others. Thus by (228) and (234), we may obtain from (97),
which will hold true of any continuous variations of phase, the
equation
vdp= —g (m1 . . . +mn) dh ; (235)
or dp=-gydh; (236)
which will therefore hold true in any mass in which equations (228)
and (234) are satisfied, and in which there are no surfaces of dis-
continuity. But the condition of equilibrium expressed by equation
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 147
(233) has no exception with respect to surfaces of discontinuity;
therefore in any mass in which such surfaces occur, it will be
necessary for equilibrium, in addition to the relations expressed by
equations (228) and (234), that there shall be no discontinuous change
of pressure at these surfaces.
This superfluity in the particular conditions of equilibrium which
we have found, as applied to a mass which is everywhere continuous
in phase, is due to the fact that we have made the elements of volume
variable in position and size, while the matter initially contained
in these elements is not supposed to be confined to them. Now, as
the different components may move in different directions when the
state of the system varies, it is evidently impossible to define the
elements of volume so as always to include the same matter; we
must, therefore, suppose the matter contained in the elements of
volume to vary ; and therefore it would be allowable to make these
elements fixed in space. If the given mass has no surfaces of discon-
tinuity, this would be much the simplest plan. But if there are any
surfaces of discontinuity, it will be possible for the state of the given
mass to vary, not only by infinitesimal changes of phase in the fixed
elements of volume, but also by movements of the surfaces of discon-
tinuity. It would therefore be necessary to add to our general
condition of equilibrium terms relating to discontinuous changes in
the elements of volume about these surfaces, — a necessity which is
avoided if we consider these elements movable, as we can then
suppose that each element remains always on the same side of the
surface of discontinuity.
Method of treating the preceding problem, in which the elements of
volume are regarded as fixed.
It may be interesting to see in detail how the particular conditions
of equilibrium may be obtained if we regard the elements of volume
as fixed in position and size, and consider the possibility of finite as
well as infinitesimal changes of phase in each element of volume. If
we use the character A to denote the differences determined by such
finite differences of phase, we may express the variation of the intrinsic
energy of the whole mass in the form
fSDe+f&De, (237)
in which the first integral extends over all the elements which are
infmitesimally varied, and the second over all those which experience
a finite variation. We may regard both integrals as extending
throughout the whole mass, but their values will be zero except for
the parts mentioned.
If we do not wish to limit ourselves to the consideration of masses
148 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
so small that the force of gravity can be regarded as constant in
direction and in intensity, we may use Y to denote the potential of
the force of gravity, and express the variation of the part of the
energy which is due to gravity in the form
-/Y 8 Dm -/Y A Dm. (238)
We shall then have, for the general condition of equilibrium,
fSDe +/AZ>e -/Y SDm -/Y ADm ^ 0 ; (239)
and the equations of condition will be
(240)
(241)
We may obtain a condition of equilibrium independent of these
equations of condition, by subtracting these equations, multiplied each
by an indeterminate constant, from condition (239). If we denote
these indeterminate constants by Ty Ml}...Mn, we shall obtain after
arranging the terms
JSDe-Y3Dm-TSDr]-MlSDml...-MnSDmn
> 0. (242)
The variations, both infinitesimal and finite, in this condition are
independent of the equations of condition (240) and (241), and are
only subject to the condition that the varied values of De, Zty,
Dmv ...Dmn for each element are determined by a certain change
of phase. But as we do not suppose the same element to experience
both a finite and an infinitesimal change of phase, we must have
SDe - Y SDm -T8Dt]-Ml 8Dm1 ...-Mn SDmn ^ 0, (243)
and &De-'YADm-T&Dr]-Ml&Dm1...-MnADmn^(). (244)
By equation (12), and in virtue of the necessary relation (222), the
first of these conditions reduces to
n^(); (245)
for which it is necessary and sufficient that
(246)
(247)
* The gravitation potential is here supposed to be defined in the usual way. But if
it were defined so as to decrease when a body falls, we should have the sign + instead
of - in these equations ; i.e., for each component, the sum of the gravitation and
intrinsic potentials would be constant throughout the whole mass.
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 149
Condition (244) may be reduced to the form
ADe-TAD;/-(Y+^1)ADm1...-(Y+^ADmn^O; (248)
and by (246) and (247) to
ADe - 1 Alty - /*! ADmx . . . - fjLn ADmn ^ 0. (249)
If values determined subsequently to the change of phase are dis-
tinguished by accents, this condition may be written
De' -tDn'- ^Dm/ . . . - yun Dmn'
-De+tDq + fjL1Dm1 . . . + fJLnDmn ^ 0, (250)
which may be reduced by (93) to
De'-tDri'-[j.lD<ml'...-iULnDmn'+pDv^O. (251)
Now if the element of volume Dv is adjacent to a surface of discon-
tinuity, let us suppose De', Drf, Dm/, . . . Dmn' to be determined (for
the same element of volume) by the phase existing on the other side
of the surface of discontinuity. As t, fa, . . . ju.n have the same values on
both sides of this surface, the condition may be reduced by (93) to
-p'Dv+pDv^O. (252)
That is, the pressure must not be greater on one side of a surface of
discontinuity than on the other.
Applied more generally, (251) expresses the condition of equilibrium
with respect to the possibility of discontinuous changes of phases at
any point. As Dv' = Dv, the condition may also be written
De' - 1 Dq +p Dv' - j^ Dm/ . . . - fj.n Dmn' ^ 0, (253)
which must hold true when t, p, fjLl} . . . fj.n have values determined
by any point in the mass, and De', Drf, Dv', Dm/, . . . Dmn' have values
determined by any possible phase of the substances of which the mass
is composed. The application of the condition is, however, subject
to the limitations considered on pages 74-79. It may easily be shown
(see page 104) that for constant values of t, fjL1} ... fj.n, and of Dv',
the first member of (253) will have the least possible value when De',
Drf, Dm/, . . . Dmn' are determined by a phase for which the tempera-
ture has the value t, and the potentials the values yUj, ... ju.n. It will
be sufficient, therefore, to consider the condition as applied to such
phases, in which case it may be reduced by (93) to
p-p'^0. (254)
That is, the pressure at any point must be as great as that of any
phase of the same components, for which the temperature and the
potentials have the same values as at that point. We may also express
this condition by saying that the pressure must be as great as is
consistent with equations (246), (247). This condition with the
equations mentioned will always be sufficient for equilibrium ; when
150 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
the condition is not satisfied, if equilibrium subsists, it will be at least
practically unstable.
Hence, the phase at any point of a fluid mass, which is in stable
equilibrium under the influence of gravity (whether this force is due
to external bodies or to the mass itself), and which has throughout the
same independently variable components, is completely determined by
the phase at any other point and the difference of the values of the
gravitational potential for the two points.
Fundamental Equations of Ideal Gases and Gas-Mixtures.
For a constant quantity of a perfect or ideal gas, the product of the
volume and pressure is proportional to the temperature, and the
variations of energy are proportional to the variations of temperature.
For a unit of such a gas we may write
pv = at,
de = c dt,
a and c denoting constants. By integration, we obtain the equation
in which E also denotes a constant. If by these equations we elimi-
nate t and p from (11) we obtain
e — E 7 a e — E 7
de — - drt --- dv,
C V G
4
de dv
or c - ^,=aw — a — .
e — E v
The integral of this equation may be written in the form
clog— - = q — alogv — H,
where H denotes a fourth constant. We may regard E as denoting the
energy of a unit of the gas for t = 0 ; H its entropy for t = 1 and v = 1 ;
a its pressure in the latter state, or its volume for t = 1 and p = 1 ;
c its specific heat at constant volume. We may extend the application
of the equation to any quantity of the gas, without altering the values
e r\ v
1U», 11 Wt5 HUUStltUUtJ
This will give
of the constants, if we substitute — , — , — for e, n, v, respectively.
m m m
, e—Em r\ „. , m /«KK\
clog = - — ZT+alog— . (25o)
cm m * v
This is a fundamental equation (see pages 85-89) for an ideal gas of
invariable composition. It will be observed that if we do not have
to consider the properties of the matter which forms the gas as
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 151
appearing in any other form or combination, but solely as constituting
the gas in question (in a state of purity), we may without loss of
generality give to E and H the value zero, or any other arbitrary
values. But when the scope of our investigations is not thus limited
we may have determined the states of the substance of the gas for
which e = 0 and ij = Q with reference to some other form in which the
substance appears, or, if the substance is compound, the states of its
components for which e = 0 and r\ = 0 may be already determined ; so
that the constants E and H cannot in general be treated as arbitrary.
We obtain from (255) by differentiation
c j 1 j aj , / CE , c+a H\j
-—-de = — dr] — dv + ( —&— + - --- -Jdm, (256)
e — Em m v \e-Em m m2/
whence, in virtue of the general relation expressed by (86),
(258>
T}). (259)
We may obtain the fundamental equation between \fs} t, v, and m
from equations (87), (255), and (257). Eliminating e we have
\fs = Em + cmt — tq,
and clog£ = — — H+alog — ;
m ' v '
and eliminating rj, we have the fundamental equation
. (260)
Differentiating this equation, we obtain
= — m(.Z/+clog£+alo£ — )dt -- dv
\ 5ra/ v
(261)
whence, by the general equation (88),
r+clog£+alog— ), (262)
frfii/
amt
p=
V '
—\ (264)
v /
152 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
From (260), by (87) and (91), we obtain
f = Em + mt( c — H— c log t + a log — J + pv,
and eliminating v by means of (263), we obtain the fundamental
equation
£=Em+mt(c+a-H~(c+a)logt+alog^. (265)
From this, by differentiation and comparison with (92), we may
obtain the equations
(266)
(267)
P
(268)
The last is also a fundamental equation. It may be written in the
form
p H—c — a , c+a, , . u — E /o«n\
— —— ' (269)
or, if we denote by e the base of the Naperian system of logarithms,
H-c-a c+a p-E
p = ae ^~t~^e~^r. (270)
The fundamental equation between x> n> P> and m may also be
easily obtained ; it is
, (271)
m
which can be solved with respect to x-
Any one of the fundamental equations (255), (260), (265), (270),
and (271), which are entirely equivalent to one another, may be
regarded as defining an ideal gas. It will be observed that most of
these equations might be abbreviated by the use of different con-
stants. In (270), for example, a single constant might be used for
H-c-a C + d
ae a , and another for - — . The equations have been given in
the above form, in order that the relations between the constants
occurring in the different equations might be most clearly exhibited.
The sum c + a is the specific heat for constant pressure, as appears if
we differentiate (266) regarding p and m as constant.*
* We may easily obtain the equation between the temperature and pressure of a
saturated vapor, if we know the fundamental equations of the substance both in the
gaseous, and in the liquid or solid state. If we suppose that the density and the specific
heat at constant pressure of the liquid may be regarded as constant quantities (for such
153
The preceding fundamental equations all apply to gases of constant
composition, for which the matter is entirely determined by a single
variable (m). We may obtain corresponding fundamental equations
for a mixture of gases, in which the proportion of the components
shall be variable, from the following considerations.
moderate pressures as the liquid experiences while in contact with the vapor), and
denote this specific heat by k, and the volume of a unit of the liquid by V, we shall
have for a unit of the liquid
t drj = k dt,
whence t\ — k log t + H',
where //' denotes a constant. Also, from this equation and (97),
d/j. = - (k log t + H') dt + Vdp,
whence M = kt - kt log t - H't +Vp + E', (A)
where E' denotes another constant. This is a fundamental equation for the substance
in the liquid state. If (268) represents the fundamental equation for the same substance
in the gaseous state, the two equations will both hold true of coexistent liquid and gas.
Eliminating fj. we obtain
p H-H' + k-c-a k-c-a, E-E' Vp
log- = logt — +— *••
6 a a a at a t
If we neglect the last term, which is evidently equal to the density of the vapor divided
by the density of the liquid, we may write
logp=A -Blogt--,
t
A, B, and G denoting constants. If we make similar suppositions in regard to the
substance in the solid state, the equation between the pressure and temperature of
coexistent solid and gaseous phases will of course have the same form.
A similar equation will also apply to the phases of an ideal gas which are coexistent
with two different kinds of solids, one of which can be formed by the combination of the
gas with the other, each being of invariable composition and of constant specific heat
and density. In this case we may write for one solid
and for the other fj^=k"t- k"t log t - H"t + V"p + E\
and for the gas fj^ — E+tl c + a-H-(c + a)logt + alog - ).
\ a/
Now if a unit of the gas unites with the quantity X of the first solid to form the
quantity 1+X of the second it will be necessary for equilibrium (see pages 67, 68) that
Substituting the values of fjt^, fj^t ^ given above, we obtain after arranging the terms
and dividing by at
when A=H+\H'-(l + \)H"-c-a-\k'
a
D (l+\)k"-\k'-c-a
—^~ -'
n E+\E'-(\+\)E"
' -
a
We may conclude from this that an equation of the same form may be applied to
an ideal gas in equilibrium with a liquid of which it forms an independently variable
component, when the specific heat and density of the liquid are entirely determined
154 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
It is a rule which admits of a very general and in many cases very
exact experimental verification, that if several liquid or solid sub-
stances which yield different gases or vapors are simultaneously in
equilibrium with a mixture of these gases (cases of chemical action
between the gases being excluded), the pressure in the gas-mixture
is equal to the sum of the pressures of the gases yielded at the same
temperature by the various liquid or solid substances taken separately.
Now the potential in any of the liquids or solids for the substance
which it yields in the form of gas has very nearly the same value
when the liquid or solid is in equilibrium with the gas-mixture as
when it is in equilibrium with its own gas alone. The difference of
the pressure in the two cases will cause a certain difference in the
values of the potential, but that this difference will be small, we may
infer from the equation
(272)
/t>m \drn t,p,m
which may be derived from equation (92). In most cases, there will
be a certain absorption by each liquid of the gases yielded by the
by its composition, except that the letters A, By C, and D must in this case be under-
stood to denote quantities which vary with the composition of the liquid. But to
consider the case more in detail, we have for the liquid by (A)
±-=ifA=kt-1etlogt- H't + Vp + E',
tn\i
where k, H', V, E' denote quantities which depend only upon the composition of the
liquid. Hence, we may write
where k, H, V, and E denote functions of m^ m2, etc. (the quantities of the several
components of the liquid). Hence, by (92),
dk . dk , dB. dV dE
T. j j :5 — ^ —
dm1 dm^ drn^ dm
If the component to which this potential relates is that which also forms the gas, we
shall have by (269)
. p H-c-a c + a,
log- = - — H --
6
a a a at
Eliminating ^ , we obtain the equation
in which A, Bt G, and D denote quantities which depend only upon the composition
of the liquid, viz. :
dS dk\
-- c-a + j — ),
dmlj
\
c-a ),
/'
j-**.\ D=~ —
'a\^ dmj' adrn^
With respect to some of the equations which have here been deduced, the reader
may compare Professor Kirchhoff " Ueber die Spannung des Dampfes von Mischungen
aus Wasser und Schwefelsaure," Pogg. Ann., vol. civ. (1858), p. 612; and Dr. Rankine
" On Saturated Vapors," Phil. Mag., vol. xxxi. (1866), p. 199.
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 155
others, but as it is well known that the above rule does not apply
to cases in which such absorption takes place to any great extent, we
may conclude that the effect of this circumstance in the cases with
which we have to do is of secondary importance. If we neglect the
slight differences in the values of the potentials due to these circum-
stances, the rule may be expressed as follows :—
The presswe in a mixture of different gases is equal to ike sum of
the pressures of the different gases as existing each by itself at the
same temperature and with the same value of its potential.
To form a precise idea of the practical significance of the law as
thus stated with reference to the equilibrium of two liquids with a
mixture of the gases which they emit, when neither liquid absorbs the
gas emitted by the other, we may imagine a long tube closed at each
end and bent in the form of a W to contain in each of the descending
loops one of the liquids, and above these liquids the gases which they
emit, viz., the separate gases at the ends of the tube, and the mixed
gases in the middle. We may suppose the whole to be in equilibrium,
the difference of the pressures of the gases being balanced by the
proper heights of the liquid columns. Now it is evident from the
principles established on pages 144-150 that the potential for either
gas will have the same value in the mixed and in the separate gas
at the same level, and therefore according to the rule in the form
which we have given, the pressure in the gas-mixture is equal to the
sum of the pressures in the separate gases, all these pressures being
measured at the same level. Now the experiments by which the rule
has been established relate rather to the gases in the vicinity of the
surfaces of the liquids. Yet, although the differences of level in these
surfaces may be considerable, the corresponding differences of pres-
sure in the columns of gas will certainly be very small in all cases
which can be regarded as falling under the laws of ideal gases, for
which very great pressures are not admitted.
If we apply the above law to a mixture of ideal gases and distin-
guish by subscript numerals the quantities relating to the different
gases, and denote by 2X the sum of all similar terms obtained by
changing the subscript numerals, we shall have by (270)
(•gj-gj-ai ci+«i Mi~-gi\ /0>7Q\
. <v "' t * e <*' ). (273)
It will be legitimate to assume this equation provisionally as the
fundamental equation defining an ideal gas-mixture, and afterwards
to justify the suitableness of such a definition by the properties which
may be deduced from it. In particular, it will be necessary to show
that an ideal gas-mixture as thus defined, when the proportion of its
components remains constant, has all the properties which have
already been assumed for an ideal gas of invariable composition; it
156 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
will also be desirable to consider more rigorously and more in detail
the equilibrium of such a gas-mixture with solids and liquids, with
respect to the above rule.
By differentiation and comparison with (98) we obtain
flj-ci-<h ci
= e ai tai e
v
ga - cg - 03 .£2
— Z = e "a t0* e
v
(275)
etc.
Equations (^75) indicate that the relation between the temperature,
the density of any component, and the potential for that component, is
not affected by the presence of the other components. They may
also be written
etc.
Eliminating fa, //2, etc. from (273) and (274) by means of (275) and
(276), we obtain
(277)
v
ri = 2j_ ( mx H1 + m^ log 1 4- m^ log - - ). (278)
\ m1/
Equation (277) expresses the familiar principle that the pressure in a
gas-mixture is equal to the sum of the pressures which the component
gases would possess if existing separately with the same volume at
the same temperature. Equation (278) expresses a similar principle
in regard to the entropy of the gas-mixture.
From (276) and (277) we may easily obtain the fundamental equa-
tion between \fs, t, v, m1} m2, etc. For by substituting in (94) the
values of p, yu1, jm2, etc. taken from these equations, we obtain
ii (c1-H1-c1\ogt+al log^1) V (279)
If we regard the proportion of the various components as constant,
this equation may be simplified by writing
m for 21m1,
cm for S1(c1m1),
wm for Z1(a1'm/1),
Em for
and Hm— am log m for
EQUILIBKIUM OF HETEROGENEOUS SUBSTANCES. 157
The values of c, a, E, and H will then be constant and m will denote
the total quantity of gas. As the equation will thus be reduced to
the form of (260), it is evident that an ideal gas-mixture, as defined
by (273) or (279), when the proportion of its components remains
unchanged, will have all the properties which we have assumed for
an ideal gas of invariable composition. The relations between the
specific heats of the gas mixture at constant volume and at constant
pressure and the specific heats of its components are expressed by
the equations m r
c = 2^, (280)
m
and . c+a=21m'<c'+ffii>. (281)
m
We have already seen that the values of t, v, m1} fa in a gas-
mixture are such as are possible for the component Q-t (to which ^
and //! relate) existing separately. If we denote by plt ijly \frlt elt \i, &
the connected values of the several quantities which the letters
indicate determined for the gas G1 as thus existing separately, and
extend this notation to the other components, we shall have by (273),
(274), and (279)
P = 21p19 9 = 2^1, ^ = 2^; (282)
whence by (87), (89), and (91)
* = 2i*i> X = 2lXl, f=2ifr (283)
The quantities p, rj, \[s, e, •%> f relating to the gas-mixture may
therefore be regarded as consisting of parts which may be attributed
to the several components in such a manner that between the parts
of these quantities which are assigned to any component, the quantity
of that component, the potential for that component, the temperature
and the volume, the same relations shall subsist as if that component
existed separately. It is in this sense that we should understand the
law of Dalton, that every gas is as a vacuum to every other gas.
It is to be remarked that these relations are consistent and possible
for a mixture of gases which are not ideal gases, and indeed without
any limitation in regard to the thermodynamic properties of the
individual gases. They are all consequences of the law that the
pressure in a mixture of different gases is equal to the sum of
the pressures of the different gases as existing each by itself at the
same temperature and with the same value of its potential. For let
Pi) n\y €i> "0"!' Xi> fi » Pz> e^c- 5 e^c- be defined as relating to the different
gases existing each by itself with the same volume, temperature, and
potential as in the gas-mixture ; if
then
158 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
and therefore, by (98), the quantity of any component gas Gl in the
gas-mixture, and in the separate gas to which plt qv etc. relate, is the
same and may be denoted by the same symbol mr Also
whence also, by (93)-(96),
All the same relations will also hold true whenever the value of \fs
for the gas-mixture is equal to the sum of the values of this function
for the several component gases existing each by itself in the same
quantity as in the gas-mixture and with the temperature and volume
of the gas-mixture. For if plt r]l} elt fa, Xi> fi> Pz> e^c- 5 e^c- are
defined as relating to the components existing thus by themselves, we
shall have
whence
Therefore, by (88), the potential //1 has the same value in the gas-
mixture and in the gas Gl existing separately as supposed. Moreover,
\ u/i< / v, m
*-
whence ^ =
Whenever different bodies are combined without communication of
work or heat between them and external bodies, the energy of the
body formed by the combination is necessarily equal to the sum of
the energies of the bodies combined. In the case of ideal gas-mixtures,
when the initial temperatures of the gas-masses which are combined
are the same (whether these gas-masses are entirely different gases,
or gas-mixtures differing only in the proportion of their components),
the condition just mentioned can only be satisfied when the tempera-
ture of the resultant gas-mixture is also the same. In such com-
binations, therefore, the final temperature will be the same as the
initial.
If we consider a vertical column of an ideal gas-mixture which is
*A subscript m after a differential coefficient relating to a body having several
independently variable components is used here and elsewhere in this paper to indicate
that each of the quantities mlt m2, etc., unless its differential occurs in the expression to
which the suffix is applied, is to be regarded as constant in the differentiation.
EQUILIBKIUM OF HETEROGENEOUS SUBSTANCES. 159
in equilibrium, and denote the densities of one of its components at
two different points by yl and y/, we shall have by (275) and (234)
Ml -Ml' ff(h'-h)
-0=e «i« =e «i< . (284)
7i
From this equation, in which we may regard the quantities distin-
guished by accents as constant, it appears that the relation between
the density of any one of the components and the height is not
affected by the presence of the other components.
The work obtained or expended in any reversible process of com-
bination or separation of ideal gas-mixtures at constant temperature,
or when the temperatures of the initial and final gas-masses and of the
only external source of heat or cold which is used are all the same,
will be found by taking the difference of the sums of the values of \{r
for the initial, and for the final gas-masses. (See pages 89, 90.) It
is evident from the form of equation (279) that this work is equal to
the sum of the quantities of work which would be obtained or
expended in producing in each different component existing separately
the same changes of density which that component experiences in the
actual process for which the work is sought.*
We will now return to the consideration of the equilibrium of a
liquid with the gas which it emits as affected by the presence of
different gases, when the gaseous mass in contact with the liquid may
be regarded as an ideal gas-mixture.
It may first be observed, that the density of the gas which is
emitted by the liquid will not be affected by the presence of other
gases which are not absorbed by the liquid, when the liquid is pro-
tected in any way from the pressure due to these additional gases.
This may be accomplished by separating the liquid and gaseous
masses by a diaphragm which is permeable to the liquid. It will
then be easy to maintain the liquid at any constant pressure which is
not greater than that in the gas. The potential in the liquid for the
substance which it yields as gas will then remain constant, and there-
fore the potential for the same substance in the gas and the density
of this substance in the gas and the part of the gaseous pressure due
to it will not be affected by the other components of the gas.
But when the gas and liquid meet under ordinary circumstances,
i.e., in a free plane surface, the pressure in both is necessarily the
same, as also the value of the potential for any common component
$r Let us suppose the density of an insoluble component of the gas
* This result has been given by Lord Rayleigh (Phil. Mag., vol. xlix., 1875, p. 311).
It will be observed that equation (279) might be deduced immediately from this
principle in connection with equation (260) which expresses the properties ordinarily
assumed for perfect gases.
160 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
to vary, while the composition of the liquid and the temperature
remain unchanged. If we denote the increments of pressure and of
the potential for 8l by dp and dfa, we shall have by (2*72)
| dp = ( -=—- J dp,
tt m VCtTTZ/j/ tt pt m
the index (L) denoting that the expressions to which it is affixed
refer to the liquid. (Expressions without such an index will refer
to the gas alone or to the gas and liquid in common.) Again, since
the gas is an ideal gas-mixture, the relation between pl and fa is
the same as if the component Sl existed by itself at the same
temperature, and therefore by (268)
Therefore ai^^Pi = \j—) dp. (285)
This may be integrated at once if we regard the differential co-
efficient in the second member as constant, which will be a very
close approximation. We may obtain a result more simple, but not
quite so accurate, if we write the equation in the form
(L> dp, (286)
where yx denotes the density of the component /S^ in the gas, and
integrate regarding this quantity also as constant. This will give
(L)
(P-P'), •; (287)
where p^ and p' denote the values of pl and p when the insoluble
component of the gas is entirely wanting. It will be observed that
p—p' is nearly equal to the pressure of the insoluble component,
in the phase of the gas-mixture to which p± relates. S1 is not
necessarily the only common component of the gas and liquid.
If there are others, we may find the increase of the part of the
pressure in the gas-mixture belonging to any one of them by
equations differing from the last only in the subscript numerals.
Let us next consider the effect of a gas which is absorbed to some
extent, and which must therefore in strictness be regarded as a com-
ponent of the liquid. We may commence by considering in general
the equilibrium of a gas-mixture of two components 81 and $2 with
a liquid formed of the same components. Using a notation like the
previous, we shall have by (98) for constant temperature,
whence (y<L> - -yjdfa = (yg - y<L) )dfi
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 161
Now if the gas is an ideal gas-mixture,
7 a* t j dp* , , aJL , dp*
d^ = -1- dp1 = -f*i and a/z2 = -^ dp2 = ^ — ,
/•v(L) \ / *v(L)\
therefore ( -£- - 1 ) dp1 = ( 1 - 2-L ) dp (288)
yi V2
We may now suppose that $j is the principal component of the
liquid, and S2 is a gas which is absorbed in the liquid to a slight
extent. In such cases it is well known that the ratio of the densities
of the substance S2 in the liquid and in the gas is for a given tempera-
ture approximately constant. If we denote this constant by A, we
shall have
,-.(L)
(289)
It would be easy to integrate this equation regarding yx as variable,
but as the variation in the value of p: is necessarily very small we
shall obtain sufficient accuracy if we regard yl as well as y\* as con-
stant. We shall thus obtain
where p^ denotes the pressure of the saturated vapor of the pure
liquid consisting of Sr It will be observed that when A = l, the
presence of the gas S2 will not affect the pressure or density of the
gas $r When A < 1, the pressure and density of the gas 8l are
greater than if $2 were absent, and when A > 1, the reverse is true.
The properties of an ideal gas-mixture (according to the definition
which we have assumed) when in equilibrium with liquids or solids
have been developed at length, because it is only in respect to these
properties that there is any variation from the properties usually
attributed to perfect gases. As the pressure of a gas saturated with
vapor is usually given as a little less than the sum of the pressure
of the gas calculated from its density and that of saturated vapor
in a space otherwise empty, while our formulae would make it a
little more, when the gas is insoluble, it would appear that in this
respect our formulae are less accurate than the rule which would
make the pressure of the gas saturated with vapor equal to the sum
of the two pressures mentioned. Yet the reader will observe that
the magnitude of the quantities concerned is not such that any
stress can be laid upon this circumstance.
It will also be observed that the statement of Dalton's law which
we have adopted, while it serves to complete the theory of gas-
mixtures (with respect to a certain class of properties), asserts nothing
G. T. L
162 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
with reference to any solid or liquid bodies. But the common rule
that the density of a gas necessary for equilibrium with a solid or
liquid is not altered by the presence of a different gas which is not
absorbed by the solid or liquid, if construed strictly, will involve
consequences in regard to solids and liquids which are entirely
inadmissible. To show this, we will assume, the correctness of the
rule mentioned. Let 8l denote the common component of the gaseous
and liquid or solid masses, and $2 the insoluble gas, and let quantities
relating to the gaseous mass be distinguished when necessary by the
index (G), and those relating to the liquid or solid by the index (L).
Now while the gas is in equilibrium with the liquid or solid, let
the quantity which it contains of 82 receive the increment dm2, its
volume and the quantity which it contains of the other component,
as well as the temperature, remaining constant. The potential for S1
in the gaseous mass will receive the increment
) ,7
dm9
v,m
and the pressure will receive the increment
( dP YG) A
*- dm.
Now the liquid or solid remaining in equilibrium with the gas must
experience the same variations in the values of //x and p. But by (272)
=
t>m~ \drn t,p,m
\dm2t)V,m
It will be observed that the first member of this equation relates
solely to the liquid or solid, and the second member solely to the
gas. Now we may suppose the same gaseous mass to be capable of
equilibrium with several different liquids or solids, and the first
member of this equation must therefore have the same value for all
such liquids or solids ; which is quite inadmissible. In the simplest
case, in which the liquid or solid is identical in substance with the
vapor which it yields, it is evident that the expression in question
denotes the reciprocal of the density of the solid or liquid. Hence,
when the gas is in equilibrium with one of its components both in the
solid and liquid states (as when a moist gas is in equilibrium with
ice and water), it would be necessary that the solid and liquid should
have the same density.
EQUILIBKIUM OF HETEROGENEOUS SUBSTANCES. 163
The foregoing considerations appear sufficient to justify the defi-
nition of an ideal gas-mixture which we have chosen. It is of course
immaterial whether we regard the definition as expressed by equation
(273), or by (279), or by any other fundamental equation which can
be derived from these.
The fundamental equations for an ideal gas-mixture corresponding
to (255), (265), and (271) may easily be derived from these equations
by using inversely the substitutions given on page 156. They are
) log X-
&l1 ll
(292)
- 2^1 ^i + a.m,) tlogt + ^a.m.t log )- (293>
The components to which the fundamental equations (273), (279),
(291), (292), (293) refer, may themselves be gas-mixtures. We may
for example apply the fundamental equations of a binary gas-mixture
to a mixture of hydrogen and air, or to any ternary gas-mixture in
which the proportion of two of the components is fixed. In fact,
the form of equation (279) which applies to a gas-mixture of any
particular number of components may easily be reduced, when the
proportions of some of these components are fixed, to the form which
applies to a gas-mixture of a smaller number of components. The
necessary substitutions will be analogous to those given on page 156.
But the components must be entirely different from one another with
respect to the gases of which they are formed by mixture. We
cannot, for example, apply equation (279) to a gas-mixture in which
the components are oxygen and air. It would indeed be easy to
form a fundamental equation for such a gas-mixture with reference
to the designated gases as components. Such an equation might be
derived from (279) by the proper substitutions, But the result would
be an equation of more complexity than (279). A chemical compound,
however, with respect to Dalton's law, and with respect to all the
equations which have been given, is to be regarded as entirely
different from its components. Thus, a mixture of hydrogen, oxygen,
and vapor of water is to be regarded as a ternary gas-mixture, having
the three components mentioned. This is certainly true when the
quantities of the compound gas and of its components are all inde-
pendently variable in the gas-mixture, without change of temperature
164 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
or pressure. Cases in which these quantities are not thus independently
variable will be considered hereafter.
Inferences in regard to Potentials in Liquids and Solids.
Such equations as (264), (268), (276), by which the values of
potentials in pure or mixed gases may be derived from quantities
capable of direct measurement, have an interest which is not confined
to the theory of gases. For as the potentials of the independently
variable components which are common to coexistent liquid and
gaseous masses have the same values in each, these expressions will
generally afford the means of determining for liquids, at least approxi-
mately, the potential for any independently variable component which
is capable of existing in the gaseous state. For although every state
of a liquid is not such as can exist in contact with a gaseous mass, it
will always be possible, when any of the components of the liquid are
volatile, to bring it by a change of pressure alone, its temperature and
composition remaining unchanged, to a state for which there is a
coexistent phase of vapor, in which the values of the potentials of the
volatile components of the liquid may be estimated from the density
of these substances in the vapor. The variations of the potentials in
the liquid due to the change of pressure will in general be quite
trifling as compared with the variations which are connected with
changes of temperature or of composition, and may moreover be
readily estimated by means of equation (272). The same consider-
ations will apply to volatile solids with respect to the determination
of the potential for the substance of the solid.
As an application of this method of determining the potentials
in liquids, let us make use of the law of Henry in regard to the
absorption of gases by liquids to determine the relation between
the quantity of the gas contained in any liquid mass and its potential.
Let us consider the liquid as in equilibrium with the gas, and let
mSG) denote the quantity of the gas existing as such, m^ the quantity
of the same substance contained in the liquid mass, fa the potential
for this substance common to the gas and liquid, v(0} and v(L) the
volumes of the gas and liquid. When the absorbed gas forms but
a very small part of the liquid mass, we have by Henry's law
m<L) XG)
(294)
where A is a function of the temperature ; and by (276)
m(G)
(295)
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 165
B and G also denoting functions of the temperature. Therefore
- (296)
It will be seen (if we disregard the difference of notation) that this
equation is equivalent in form to (216), which was deduced from
a priori considerations as a probable relation between the quantity
and the potential of a small component. When a liquid absorbs
several gases at once, there will be several equations of the form of
(296), which will hold true simultaneously, and which we may regard
as equivalent to equations (217), (218). The quantities A and C in
(216), with the corresponding quantities in (217), (218), were regarded
as functions of the temperature and pressure, but since the potentials
in liquids are but little affected by the pressure, we might anticipate
that these quantities in the case of liquids might be regarded as
functions of the temperature alone.
In regard to equations (216), (217), (218), we may now observe
that by (264) and (276) they are shown to hold true in ideal gases or
gas-mixtures, not only for components which form only a small part
of the whole gas-mixture, but without any such limitation, and not
only approximately but absolutely. It is noticeable that in this case
quantities A and C are functions of the temperature alone, and do
not even depend upon the nature of the gaseous mass, except upon
the particular component to which they relate. As all gaseous bodies
are generally supposed to approximate to the laws of ideal gases when
sufficiently rarefied, we may regard these equations as approximately
valid for gaseous bodies in general when the density is sufficiently
small. When the density of the gaseous mass is very great, but
the separate density of the component in question is small, the
equations will probably hold true, but the values of A and G may
not be entirely independent of the pressure, or of the composition
of the mass in respect to its principal components. These equations
will also apply, as we have just seen, to the potentials in liquid
bodies for components of which the density in the liquid is very
small, whenever these components exist also in the gaseous state,
and conform to the law of Henry. This seems to indicate that the
law expressed by these equations has a very general application.
Considerations relating to the Increase of Entropy due to the
Mixture of Gases by Diffusion.
From equations (278) we may easily calculate the increase of
entropy which takes place when two different gases are mixed by
diffusion, at a constant temperature and pressure. Let us suppose
166 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
that the quantities of the gases are such that each occupies initially
one half of the total volume. If we denote this volume by V, the
increase of entropy will be
V V
or (ra^ -f m2a2) log 2.
xr Pv
Now m-r and wa
Therefore the increase of entropy may be represented by the
expression
(297)
It is noticeable that the value of this expression does not depend
upon the kinds of gas which are concerned, if the quantities are such
as has been supposed, except that the gases which are mixed must
be of different kinds. If we should bring into contact two masses
of the same kind of gas, they would also mix, but there would be
no increase of entropy. But in regard to the relation which this
case bears to the preceding, we must bear in mind the following
considerations. When we say that when two different gases mix by
diffusion, as we have supposed, the energy of the whole remains
constant, and the entropy receives a certain increase, we mean that
the gases could be separated and brought to the same volume and
temperature which they had at first by means of certain changes in
external bodies, for example, by the passage of a certain amount of
heat from a warmer to a colder body. But when we say that when
two gas-masses of the same kind are mixed under similar circum-
stances there is no change of energy or entropy, we do not mean
that the gases which have been mixed can be separated without
change to external bodies. On the contrary, the separation of the
gases is entirely impossible. We call the energy and entropy of the
gas-masses when mixed the same as when they were unmixed,
because we do not recognize any difference in the substance of the
two masses. So when gases of different kinds are mixed, if we ask
what changes in external bodies are necessary to bring the system
to its original state, we do not mean a state in which each particle
shall occupy more or less exactly the same position as at some
previous epoch, but only a state which shall be undistinguishable
from the previous one in its sensible properties. It is to states of
systems thus incompletely defined that the problems of thermo-
dynamics relate.
But if such considerations explain why the mixture of gas-masses
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 167
of the same kind stands on a different footing from the mixture of
gas-masses of different kinds, the fact is not less significant that the
increase of entropy due to the mixture of gases of different kinds,
in such a case as we have supposed, is independent of the nature of
the gases.
Now we may without violence to the general laws of gases which
are embodied in our equations suppose other gases to exist than such
as actually do exist, and there does not appear to be any limit to the
resemblance which there might be between two such kinds of gas.
But the increase of entropy due to the mixing of given volumes of the
gases at a given temperature and pressure would be independent of
the degree of similarity or dissimilarity between them. We might also
imagine the case of two gases which should be absolutely identical
in all the properties (sensible and molecular) which come into play
while they exist as gases either pure or mixed with each other,
but which should differ in respect to the attractions between their
atoms and the atoms of some other substances, and therefore in their
tendency to combine with such substances. In the mixture of such
gases by diffusion an increase of entropy would take place, although
the process of mixture, dynamically considered, might be absolutely
identical in its minutest details (even with respect to the precise
path of each atom) with processes which might take place without
any increase of entropy. In such respects, entropy stands strongly
contrasted with energy. Again, when such gases have been mixed,
there is no more impossibility of the separation of the two kinds
of molecules in virtue of their ordinary motions in the gaseous mass
without any especial external influence, than there is of the separation
of a homogeneous gas into the same two parts into which it has once
been divided, after these have once been mixed. In other words, the
impossibility of an uncompensated decrease of entropy seems to be
reduced to improbability.
There is perhaps no fact in the molecular theory of gases so well
established as that the number of molecules in a given volume at a
given temperature and pressure is the same for every kind of gas
when in a state to which the laws of ideal gases apply. Hence the
quantity *y- in (297) must be entirely determined by the number of
L
molecules which are mixed. And the increase of entropy is therefore
determined by the number of these molecules and is independent of
their dynamical condition and of the degree of difference between
them.
The result is of the same nature when the volumes of the gases
which are mixed are not equal, and when more than two kinds of
gas are mixed. If we denote by vlf v2, etc., the initial volumes of the
168 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
different kinds of gas, and by V as before the total volume, the
increase of entropy may be written in the form
^(ra^j) log F— S1(m1a1 log vj.
And if we denote by rl}rz, etc., the numbers of the molecules of the
several different kinds of gas, we shall have
rj = Cm^ , r2 = (7ra2a2 , etc.,
where G denotes a constant. Hence
vl : V : : m^ : ^(m^) : : rx : 2^ ;
and the increase of entropy may be written
2^*1 log Siri-Sifo log rj
~~C~
The Phases of Dissipated Energy of an Ideal Gas-mixture with
Components which are Chemically Related.
We will now pass to the consideration of the phases of dissipated
energy (see page 140) of an ideal gas-mixture, in which the number
of the proximate components exceeds that of the ultimate.
Let us first suppose that an ideal gas-mixture has for proximate
components the gases GI} 6r2, and 6r3, the units of which are denoted
by ©,, ©o, ($o, and that in ultimate analysis
tr A * « ' O ' t/
'" " . ."; . , ®3 = X1©1+X2©2, . (299)
\! and X2 denoting positive constants, such that X1 + X2 = 1. . The
phases which we are to consider are those for which the energy of
the gas-mixture is a minimum for constant entropy and volume and
constant quantities of G1 and 6r2, as determined in ultimate analysis.
For such phases, by (86), . ...
fa Sm1 + fa Smz + JULB Sm3 ^ 0 (300)
for such values of the variations as do not affect the quantities of
G1 and 6r2 as determined in ultimate analysis. Values of Sm1} <5m2,
(Sm3 proportional to X1? X2, — 1, and only such, are evidently consistent
with this restriction : therefore
X1/z1+X2^2 = ^3. (301)
If we substitute in this equation values of fa, fi2) /*3 taken from
(276), we obtain, after arranging the terms and dividing by t,
^ 1 mi i x 1 m<> l ms A , r»i 0 /o^n\
\ai^-^+^2l^~-^^S-^ *=A+Blogt-j, (302)
where
(303)
(304)
(305)
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 169
If we denote by fa and fa the volumes (determined under standard
conditions of temperature and pressure) of the quantities of the gases
Gl and G2 which are contained in a unit of volume of the gas Gs, we
shall have
/-I AI Ot-i j /•» AoOto /OA/3\
fa — - -, and /32 = ^— % (306)
3 3
and (302) will reduce to the form
& nnrt -nj3i+/3o-l n n ^ n t* ^ '
a3 a3
Moreover, as by (277)
^v=(a1m1+a2m2+a3m3X, (308)
we have on eliminating v
A . B', , C /OAA\
T = — — log* -- 7, (309)
-]
where B/ = \cl-i-\cz — c^-\-\lal+\2a2 — a^ (310)
It will be observed that the quantities fa, fa wl^ always be posi-
tive and have a simple relation to unity, and that the value of
fa+fa — 1 will be positive or zero, according as gas G3 is formed
of G, and G9 with or without condensation. If we should assume,
1 4
according to the rule often given for the specific heat of compound
gases, that the thermal capacity at constant volume of any quantity
of the gas 6r3 is equal to the sum of the thermal capacities of the
quantities which it contains of the gases Gl and 6r2, the value of B
would be zero. The heat evolved in the formation of a unit of the gas
Gr3 out of the gases Gt and G2, without mechanical action, is by
(283) and (257)
or Bt + C,
which will reduce to C when the above relation in regard to the
specific heats is satisfied. In any case the quantity of heat thus
evolved divided by aBt2 will be equal to the differential coefficient of
the second member of equation (307) with respect to t. Moreover,
the heat evolved in the formation of a unit of the gas G3 out of the
gases G1 and G2 under constant pressure is
which is equal to the differential coefficient of jbhe second member of
(309) with respect to t, multiplied by a^t2.
It appears by (307) that, except in the case when fa+fa = I,
for any given finite values of m1, m2, m3, and t (infinitesimal values
being excluded as well as infinite), it will always be possible to
assign such a finite value to v that the mixture shall be in a state
170 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
of dissipated energy. Thus, if we regard a mixture of hydrogen
oxygen, and vapor of water as an ideal gas-mixture, for a mixture
containing any given quantities of these three gases at any given
temperature there will be a certain volume at which the mixture will be
in a state of dissipated energy. In such a state no such phenomenon
as explosion will be possible, and no formation of water by the action
of platinum. (If the mass should be expanded beyond this volume,
the only possible action of a catalytic agent would be to resolve the
water into its components.) It may indeed be true that at ordinary
temperatures, except when the quantity either of hydrogen or of
oxygen is very small compared with the quantity of water, the state
of dissipated energy is one of such extreme rarefaction as to lie
entirely beyond our power of experimental verification. It is also to
be noticed that a state of great rarefaction is so unfavorable to any
condensation of the gases, that it is quite probable that the catalytic
action of platinum may cease entirely at a degree of rarefaction far
short of what is necessary for a state of dissipated energy. But with
respect to the theoretical demonstration, such states of great rarefac-
tion are precisely those to which we should suppose that the laws of
ideal gas-mixtures would apply most perfectly.
But when the compound gas G3 is formed of G-^ and G2 without
condensation (i.e., when ^+^ = 1), it appears from equation (307)
that the relation between mlt m2, and m3 which is necessary for a
phase of dissipated energy is determined by the temperature alone.
In any case, if we regard the total quantities of the gases 6^ and
G2 (as determined by the ultimate analysis of the gas-mixture), and
also the volume, as constant, the quantities of these gases which
appear uncombined in a phase of dissipated energy will increase with
the temperature, if the formation of the compound G3 without
change of volume is attended with evolution of heat. Also, if we
regard the total quantities of the gases G± and G2, and also the
pressure, as constant, the quantities of these gases which appear un-
combined in a phase of dissipated energy, will increase with the
temperature, if the formation of the compound G3 under constant
pressure is attended with evolution of heat. If B = Q (a case, as
has been seen, of especial importance), the heat obtained by the
formation of a unit of G3 out of Gl and G2 without change of volume
or of temperature will be equal to G. If this quantity is positive,
and the total quantities of the gases Gl and G2 and also the volume
have given finite values, for an infinitesimal value of t we shall have
(for a phase of dissipated energy) an infinitesimal value either of ^
or of m2, and for an infinite value of t we shall have finite (neither in-
finitesimal nor infinite) values of m1, m2, and m3. But if we suppose
the pressure instead of the volume to have a given finite value (with
EQUILIBKIUM OF HETEROGENEOUS SUBSTANCES. 171
suppositions otherwise the same), we shall have for infinitesimal
values of t an infinitesimal value either of ml or m2, and for infinite
values of t finite or infinitesimal values of ra3 according as /31 + #2
is equal to or greater than unity.
The case which we have considered is that of a ternary gas-mixture,
but our results may easily be generalized in this respect. In fact,
whatever the number of component gases in a gas-mixture, if there
are relations of equivalence in ultimate analysis between these com-
ponents, such relations may be expressed by one or more equations of
the form
A^+A^+As^g+etc^O, (311)
where ($1} ®2, etc. denote the units of the various component gases,
and A15 A2, etc. denote positive or negative constants such that
2^ = 0. From (311) with (86) we may derive for phases of dis-
sipated energy,
A!//! + A2yu2 + A3//3 + etc. = 0,
or 21(A1//1) = 0. (312)
Hence, by (276),
(313)
where A, B and C are constants determined by the equations
A = ^(AA - \fr - A^), (314)
1), (315)
1). (316)
Also, since pv = 21(alml)t,
2j (A^ log m^ — 2^04) log S^Ojmj)
+ 2(\lal)logp = A+B'\ogt-j, (317)
where -B^S^X^+X^ (318)
If there is more than one equation of the form (311), we shall have
more than one of each of the forms (313) and (317), which will hold
true simultaneously for phases of dissipated energy.
It will be observed that the relations necessary for a phase of dis-
sipated energy between the volume and temperature of an ideal gas-
mixture, and the quantities of the components which take part in the
chemical processes, and the pressure due to these components, are not
affected by the presence of neutral gases in the gas-mixture.
From equations (312) and (234) it follows that if there is a phase of
dissipated energy at any point in an ideal gas-mixture in equilibrium
under the influence of gravity, the whole gas-mixture must consist of
such phases.
172 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
The equations of the phases of dissipated energy of a binary gas-
mixture, the components of which are identical in substance, are
comparatively simple in form. In this case the two components have
the same potential, and if we write /3 for — (the ratio of the volumes
&2
of equal quantities of the two components under the same conditions
of temperature and pressure), we shall have
mJ* A B , , G /QIQ\
log- -1-^ = — -\ — lost -- T, (319)
&ra2t>0- a2 a2 a2t'
m^p?-1 A , B' C /Qom
log — -r- — xft-i= — H — l°g£ -- ;5 (320)
&p-
where A = H1 — H2 — q + Cg— a^a^ (321)
^ = cx — c2, B/ = c1—-c2-\-al — a2, (322)
C=El-E2. (323)
Gas-mixtures with Convertible Components.
The equations of the phases of dissipated energy of ideal gas-mixtures
which have components of which some are identical in ultimate
analysis to others have an especial interest in relation to the theory of
gas-mixtures in which the components are not only thus equivalent,
but are actually transformed into each other within the gas-mixture
on variations of temperature and pressure, so that quantities of these
(proximate) components are entirely determined, at least in any per-
manent phase of the gas-mixture, by the quantities of a smaller
number of ultimate components, with the temperature and pressure.
Such gas-mixtures may be distinguished as having convertible com-
ponents. The very general considerations adduced on pages 138-144,
which are not limited in their application to gaseous bodies, suggest
the hypothesis that the equations of the phases of dissipated energy
of ideal gas-mixtures may apply to such gas-mixtures as have been
described. It will, however, be desirable to consider the matter more
in detail.
In the first place, if we consider the case of a gas-mixture which
only differs from an ordinary ideal gas-mixture for which some of the
components are equivalent in that there is perfect freedom in regard
to the transformation of these components, it follows at once from the
general formula of equilibrium (1) or (2) that equilibrium is only
possible for such phases as we have called phases of dissipated energy,
for which some of the characteristic equations have been deduced in
the preceding pages.
If it should be urged, that regarding a gas-mixture which has con-
vertible components as an ideal gas-mixture of which, for some reason,
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 173
only a part of the phases are actually capable of existing, we might
still suppose the particular phases which alone can exist to be deter-
mined by some other principle than that of the free convertibility
of the components (as if, perhaps, the case were analogous to one of
constraint in mechanics), it may easily be shown that such a hypothesis
is entirely untenable, when the quantities of the proximate components
may be varied independently by suitable variations of the temperature
and pressure, and of the quantities of the ultimate components, and
it is admitted that the relations between the energy, entropy, volume,
temperature, pressure, and the quantities of the several proximate
components in the gas-mixture are the same as for an ordinary ideal
gas-mixture, in which the components are not convertible. Let us
denote the quantities of the ri proximate components of a gas-mixture
A by m^ mz, etc., and the quantities of its n ultimate components by
mlt m2, etc. (n denoting a number less than n'), and let us suppose
that for this gas-mixture the quantities e, ?/, v, t, p, m1? m2, etc. satisfy
the relations characteristic of an ideal gas-mixture, while the phase of
the gas-mixture is entirely determined by the values of m1} n^, etc.,
with two of the quantities e, 77, v, t, p. We may evidently imagine
such an ideal gas-mixture B having n' components (not convertible),
that every phase of A shall correspond with one of B in the values of
e, q, v, t, p, mx, m2, etc. Now let us give to the quantities m1, m2, etc.
in the gas-mixture A any fixed values, and for the body thus defined
let us imagine the v-q-e surface (see page 116) constructed; likewise
for the ideal gas-mixture B let us imagine the v-q-e surface constructed
for every set of values of m1? ra2, etc. which is consistent with the
given values of m^ m2, etc., i.e., for every body of which the ultimate
composition would be expressed by the given values of m1,m2, etc. It
follows immediately from our supposition, that every point in the
v-jj-6 surface relating to A must coincide with some point of one of
the v-rj-e surfaces relating to B not only in respect to position but also
in respect to its tangent plane (which represents temperature and
pressure) ; therefore the v-r\-e surface relating to A must be tangent to
the various v-q-€ surfaces relating to B, and therefore must be an
envelop of these surfaces. From this it follows that the points which
represent phases common to both gas-mixtures must represent the
phases of dissipated energy of the gas-mixture B.
The properties of an ideal gas-mixture which are assumed in regard
to the gas-mixture of convertible components in the above demonstra-
tion are expressed by equations (277) and (278) with the equation
e = Itl(c1m1t+mlE1). (324)
It is usual to assume in regard to gas-mixtures having convertible
components that the convertibility of the components does not affect
174 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
the relations (277) and (324). The same cannot be said of the equation
(278). But in a very important class of cases it will be sufficient if
the applicability of (277) and (324) is admitted. The cases referred to
are those in which in certain phases of a gas-mixture the components
are convertible, and in other phases of the same proximate composition
the components are not convertible, and the equations of an ideal gas-
mixture hold true.
If there is only a single degree of convertibility between the com-
ponents (i.e., if only a single kind of conversion, with its reverse, can
take place among the components), it will be sufficient to assume, in
regard to the phases in which conversion takes place, the validity of
equation (277) and of the following, which can be derived from (324)
by differentiation, and comparison with equation (11), which expresses
a necessary relation,
[t drj -p dv - ^fernO dt]M = 0.* (325)
We shall confine our demonstration to this case. It will be observed
that the physical signification of (325) is that if the gas-mixture is
subjected to such changes of volume and temperature as do not
alter its proximate composition, the heat absorbed or yielded may
be calculated by the same formula as if the components were not
convertible.
Let us suppose the thermodynamic state of a gaseous mass M, of
such a kind as has just been described, to be varied while within
the limits within which the components are not convertible. (The
quantities of the proximate components, therefore, as well as of the
ultimate, are supposed constant.) If we use the same method of
geometrical representation as before, the point representing the volume,
entropy, and energy of the mass will describe a line in the v-q-e
surface of an ideal gas-mixture of inconvertible components, the form
and position of this surface being determined by the proximate com-
position of M. Let us now suppose the same mass to be carried
beyond the limit of inconvertibility, the variations of state after
passing the limit being such as not to alter its proximate composition.
It is evident that this will in general be possible. Exceptions can
only occur when the limit is formed by phases in which the proximate
composition is uniform. The line traced in the region of convertibility
must belong to the same v-q-e surface of an ideal gas-mixture of
inconvertible components as before, continued beyond the limit
of inconvertibility for the components of M, since the variations of
volume, entropy, and energy are the same as would be possible if the
components were not convertible. But it must also belong to the
v-ij-e surface of the body M, which is here a gas-mixture of con-
* This notation is intended to indicate that 7% , w2 , etc. are regarded as constant.
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 175
vertible components. Moreover, as the inclination of each of these
surfaces must indicate the temperature and pressure of the phases
through which the body passes, these two surfaces must be tangent
to each other along the line which has been traced. As the v-q-e
surface of the body M in the region of convertibility must thus be
tangent to all the surfaces representing ideal gas-mixtures of every
possible proximate composition consistent with the ultimate composi-
tion of M, continued beyond the region of inconvertibility, in which
alone their form and position may be capable of experimental demon-
stration, the former surface must be an envelop of the latter surfaces,
and therefore a continuation of the surface of the phases of dissipated
energy in the region of inconvertibility.
The foregoing considerations may give a measure of a priori
probability to the results which are obtained by applying the ordinary
laws of ideal gas-mixtures to cases in which the components are con-
vertible. It is only by experiments upon gases in phases in which
their components are convertible that the validity of any of these
results can be established.
The very accurate determinations of density which have been made
for the peroxide of nitrogen enable us to subject some of our equations
to a very critical test. That this substance in the gaseous state is
properly regarded as a mixture of different gases can hardly be
doubted, as the proportion of the components derived from its density
on the supposition that one component has the molecular formula NO2
and the other the formula N2O4 is the same as that derived from the
depth of the color on the supposition that the absorption of light is
due to one of the components alone, and is proportioned to the separate
density of that component.*
MM. Sainte-Claire Deville and Troost^ have given a series of
determinations of what we shall call the relative densities of peroxide
of nitrogen at various temperatures under atmospheric pressure. We
use the term relative density to denote what it is usual in treatises on
chemistry to denote by the term density, viz., the actual density of a
gas divided by the density of a standard perfect gas at the same
pressure and temperature, the standard gas being air, or more strictly,
an ideal gas which has the same density as air at the zero of the
centigrade scale and the pressure of one atmosphere. In order to test
our equations by these determinations, it will be convenient to trans-
form equation (320), so as to give directly the relation between the
relative density, the pressure, and the temperature.
As the density of the standard gas at any given temperature and
*Salet, "Sur la coloration du peroxyde d'azote," Comptes Rendus, vol. Ixvii. p. 488.
t Gomptes Rendus, vol. Ixiv. p. 237.
176 EQUILIBRIUM OF HETEEOGENEOUS SUBSTANCES.
pressure may by (263) be expressed by the formula —, the relative
density of a binary gas-mixture may be expressed by
n.t.
(326)
JJV
Now by (263) a.m, + a2m2 =^. (327)
L
By giving to m2 and ma successively the value zero in these equations,
we obtain
A=2s, A=A (328)
«<! U<2
where D1 and D2 denote the values of D when the gas consists wholly
of one or of the other component. If we assume that
A = 2A, (329)
we shall have a1 = 2a2. (330)
From (326) we have m, + m2 = D ,
ast
and from (327), by (328) and (330),
whence mi = (A-£) (331)
(332)
By (327), (331), and (332) we obtain from (320)
A , B' C ,QQQx
= — — log^ -- :• (333)
T
2 (D - D^a, a2
This formula will be more convenient for purposes of calculation if
we introduce common logarithms (denoted by Iog10) instead of hyper-
bolic, the temperature of the ordinary centigrade scale tc instead of
the absolute temperature t, and the pressure in atmospheres pat instead
of p the pressure in a rational system of units. If we also add the
logarithm of as to both sides of the equation, we obtain
where A and 0 denote constants, the values of which are closely
connected with those of A and G.
From the molecular formulae of peroxide of nitrogen N02 and
N204, we may calculate the relative densities
= 1-589, and A = *0691 = 3'178. (335)
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 177
The determinations of MM. Deville and Troost are satisfactorily
represented by the equation
(3178 -D)*pat , 3118-6
which gives D = 3178 + 9- V9(3178 + 9),
where Iog10 9 = 9'47056 -
In the first part of the following table are given in successive
columns the temperature and pressure of the gas in the several
experiments of MM. Deville and Troost, the relative densities calcu-
lated from these numbers by equation (336), the relative densities
as observed, and the difference of the observed and calculated relative
densities. It will be observed that these differences are quite small,
in no case reaching '03, and on the average scarcely exceeding -01.
The significance of such correspondence in favour of the hypothesis
by means of which equation (336) has been established is of course
diminished, by the fact that two constants in the equation have been
determined from these experiments. If the same equation can be
shown to give correctly the relative densities at other pressures than
that for which the constants have been determined, such correspon-
dence will be much more decisive.
D
fc
Pat
calculated
D
diff.
Observers.
by eq. (336).
observed.
26-7
1
2-676
2-65
-•026
D.&T.
35-4
1
2-524
2-53
+ •006
D. &T.
39-8
1
2-443
2-46
+ •017
D.&T.
49'6
1
2-256
2-27
+ •014
D.&T.
60-2
1
2-067
2-08
+ •013
D.&T.
70-0
1
1-920
1-92
•000
D.&T.
80-6
1
1-801
1-80
-•001
D.&T.
90-0
1
1-728
1-72
-•008
D.&T.
100-1
1
1-676
1-68
+ •004
D.&T.
111-3
1
1-641
1-65
+ •009
D.&T.
121-5
1
1-622
1-62
-•002
D.&T.
135-0
1
1-607
1-60
-•007
D.&T.
154-0
1
1-597
1-58
-•017
D.&T.
183-2
1
1-592
1-57
-•022
D.&T.
97-5
1
1-687
97-5
10480
<re~5tT
1-631
1-783
+ •152
R&W.
24-5
1
2-711
24-5
18090
12R2U
2-524
2-52
-•004
P. &W.
11-8
1
2-891
11-3
&th
2-620
2-645
+ •025
P. &W.
4-2
1
2-964
4-2
^sWV
2-708
2-588
-•120
P. &W.
Messrs. Play fair and Wanklyn have published* four determinations
of the relative density of peroxide of nitrogen at various temperatures
* Transactions of the Royal Society of Edinburgh, vol. xxii. p. 441.
G. I. M
178 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
when diluted with nitrogen. Since the relations expressed by equa-
tions (319) and (320) are not affected by the presence of a third gas
which is different from the gases Gl and 6r2 (to which mx and m2
relate) and neutral to them (see the remark at the foot of page 171),
— provided that we take p to denote the pressure which we attribute
to the gases Gl and G2, i.e., the total pressure diminished by the
pressure which the third gas would exert if occupying alone the
same space at the same temperature, — it follows that the relations
expressed for peroxide of nitrogen by (333), (334), and (336) will
not be affected by the presence of free nitrogen, if the pressure
expressed by p or pat and contained implicitly in the symbol D (see
equation (326) by which D is defined) is understood to denote the
total pressure diminished by the pressure due to the free nitrogen.
The determinations of Playfair and Wanklyn are given in the latter
part of the above table. The pressures given are those obtained by
subtracting the pressure due to the free nitrogen from the total
pressure. We may suppose such reduced pressures to have been
used in the reduction of the observations by which the numbers
in the column of observed relative densities were obtained. Besides
the relative densities calculated by equation (336) for the temperatures
and (reduced) pressures of the observations, the table contains the
relative densities calculated for the same temperatures and the pressure
of one atmosphere.
The reader will observe that in the second and third experiments
of Playfair and Wanklyn there is a very close accordance between
the calculated and observed values of D, while in the second and
fourth experiments there is a considerable difference. Now the weight
to be attributed to the several determinations is very different. The
quantities of peroxide of nitrogen which were used in the several
experiments were respectively '2410, *5893, '3166, and '2016 grammes.
For a rough approximation, we may assume that the probable errors
of the relative densities are inversely proportional to these numbers.
This would make the probable error of the first and fourth observations
two or three times as great as that of the second and considerably
greater than that of the third. We must also observe that in the
first of these experiments, the observed relative density 1*783 is
greater than 1*687, the relative density calculated by equation (336)
for the temperature of the experiment and the pressure of one
atmosphere. Now the number 1*687 we may regard as established
directly by the experiments of Deville and Troost. For in seven
successive experiments in this part of the series the calculated relative
densities differ from the observed by less than *01. If then we accept
the numbers given by experiment, the effect of diluting the gas with
nitrogen is to increase its relative density. As this result is entirely
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 179
at variance with the facts observed in the case of other gases, and
in the case of this gas at lower temperatures, as appears from the
three other determinations of Playfair and Wanklyn, it cannot possibly
be admitted on the strength of a single observation. The first experi-
ment of this series cannot therefore properly be used as a test of our
equations. Similar considerations apply with somewhat less force to
the last experiment. By comparing the temperatures and pressures
of the three last experiments with the observed relative densities, the
reader may easily convince himself that if we admit the substantial
accuracy of the determinations in the two first of these experiments
(the second and third of the series, which have the greatest weight)
the last determination of relative density 2 '588 must be too small. In
fact, it should evidently be greater than the number in the preceding
experiment 2'645.
If we confine our attention to the second and third experiments of
the series, the agreement is as good as could be desired. Nor will
the admission of errors of '152 and '120 (certainly not large in deter-
minations of this kind) in the first and fourth experiments involve
any serious doubt of the substantial accuracy of the second and third,
when the difference of weight of the determinations is considered.
Yet it is much to be desired that the relation expressed by (336), or
with more generality by (334), should be tested by more numerous
experiments.
It should be stated that the numbers in the column of pressures
are not quite accurate. In the experiments of Deville and Troost
the gas was subject to the actual atmospheric pressure at the time of
the experiment. This varied from 747 to 764 millimeters of mercury.
The precise pressure for each experiment is not given. In the
experiments of Playfair and Wanklyn the mixture of nitrogen and
peroxide of nitrogen was subject to the actual atmospheric pressure
at the time of the experiment. The numbers in the column of pres-
sures express the fraction of the whole pressure which remains after
subtracting the part due to the free nitrogen. But no indication is
given in the published account of the experiments in regard to the
height of the barometer. Now it may easily be shown that a varia-
tion of n^ in the value of p can in no case cause a variation of more
than "005 in the value of D as calculated by equation (336). In any
of the experiments of Playfair and Wanklyn a variation of more than
3Qmm in the height of the barometer would be necessary to produce
a variation of '01 in the value of D. The errors due to this source
cannot therefore be very serious. They might have been avoided
altogether in the discussion of the experiments of Deville and Troost
by using instead of (336) a formula expressing the relation between
the relative density, the temperature, and the actual density, as the
180 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
reciprocal of the latter quantity is given for each experiment of
this series. It seemed best, however, to make a trifling sacrifice of
accuracy for the sake of simplicity.
It might be thought that the experiments under discussion would
be better represented by a formula in which the term containing log t
(see equation (333)) was retained. But an examination of the figures
in the table will show that nothing important can be gained in this
respect, and there is hardly sufficient motive for adding another term
to the formula of calculation. Any attempt to determine the real
values of A, H and C in equation (333) (assuming the absolute
validity of such an equation for peroxide of nitrogen), from the
experiments under discussion would be entirely misleading, as the
reader may easily convince himself.
From equation (336), however, the following conclusions may be
deduced. By comparison with (334) we obtain
,£', C Q,,-n,r 3118-6
A+— log10*-T = 9-47056 -- - — ,
1*2 v v
which must hold true approximately between the temperatures 11°
and 90C. (At higher temperatures the relative densities vary too
slowly with the temperatures to afford a critical test of the accuracy
of this relation.) By differentiation we obtain
MB' C_ 3118-6
a2t + t*~ tz
where M denotes the modulus of the common system of logarithms.
Now by comparing equations (333) and (334) we see that
Hence
which may be regarded as a close approximation at 40° or 50°, and
a tolerable approximation between the limits of temperature above
mentioned. Now B't-\-C represents the heat evolved by the con-
version of a unit of N02 into N2O4 under constant pressure. Such
conversion cannot take place at constant pressure without change of
temperature, which renders the experimental verification of the last
equation less simple. But since by equations (322)
we shall have for the temperature of 40C
Now Bt + C represents the decrease of energy when a unit of N02 is
transformed into N204 without change of temperature. It therefore
EQUILIBKIUM OF HETEROGENEOUS SUBSTANCES. 181
represents the excess of the heat evolved over the work done by
external forces when a mass of the gas is compressed at constant
temperature until a unit of NO2 has been converted into N2O4.
This quantity will be constant if .6 = 0, i.e., if the specific heats at
constant volume of NO2 and N2O4 are the same. This assumption
would be more simple from a theoretical stand-point and perhaps
safer than the assumption that & = Q. If B = 0, H = a2. If we wish
to embody this assumption in the equation between D, p, and t, we
may substitute
for the second member of equation (336). The relative densities
calculated by the equation thus modified from the temperatures and
pressures of the experiments under discussion will not differ from
those calculated from the unmodified equation by more than '002 in
any case, or by more than '001 in the first series of experiments.
It is to be noticed that if we admit the validity of the volumetrical
relation expressed by equation (333), which is evidently equivalent to
an equation between p, t, v, and ra (this letter denoting the quantity
of the gas without reference to its molecular condition), or if we admit
the validity of the equation only between certain limits of temperature
and for densities less than a certain limit of density, and also admit
that between the given limits of temperature the specific heat of the
gas at constant volume may be regarded as a constant quantity when
the gas is sufficiently rarefied to be regarded as consisting wholly of
NO2, — or, to speak without reference to the molecular state of the gas,
when it is rarefied until its relative density D approximates to its
limiting value Dv — we must also admit the validity (within the same
limits of temperature and density) of all the calorimetrical relations
which belong to ideal gas-mixtures with convertible components. The
premises are evidently equivalent to this, — that we may imagine an
ideal gas with convertible components such that between certain
limits of temperature and above a certain limit of density the relation
between p, t, and v shall be the same for a unit of this ideal gas as for
a unit of peroxide of nitrogen, and for a very great value of v (within
the given limits of temperature) the thermal capacity at constant
volume of the ideal and actual gases shall be the same. Let us regard
t and v as independent variables ; we may let these letters and p refer
alike to the ideal and real gases, but we must distinguish the entropy
r\ of the ideal gas from the entropy r\ of the real gas. Now by (88)
dv
therefore *******
dv dt ~dt dv~dt dt ~~ dt2'
(338)
182 EQUILIBRIUM OF HETEEOGENEOUS SUBSTANCES.
Since a similar relation will hold true for r\ ', we obtain
d_drj_dL<ty
dvdfdvdt'
which must hold true within the given limits of temperature and
density. Now it is granted that
for very great values of v at any temperature within the given limits
(for the two members of the equation represent the thermal capacities
at constant volume of the real and ideal gases divided by t), hence,
in virtue of (339), this equation must hold true in general within the
given limits of temperature and density. Again, as an equation like
(337) will hold true of r[t we shall have
dH = <W_ (341)
dv dv'
From the two last equations it is evident that in all calorimetrical
relations the ideal and real gases are identical. Moreover the energy
and entropy of the ideal gas are evidently so far arbitrary that we
may suppose them to have the same values as in the real gas for any
given values of t and v. Hence the entropies of the two gases are
the same within the given limits; and on account of the necessary
relation
de — tdri —p dv,
the energies of the two gases are in like manner identical. Hence
the fundamental equation between the energy, entropy, volume, and
quantity of matter must be the same for the ideal gas as for the
actual.
We may easily form a fundamental equation for an ideal gas-
mixture with convertible components, which shall relate only to the
phases of equilibrium. For this purpose, we may use the equations
of the form (312) to eliminate from the equation of the form (273),
which expresses the relation between the pressure, the temperature,
and the potentials for the proximate components, as many of the
potentials as there are equations of the former kind, leaving the
potentials for those components which it is convenient to regard as
the ultimate components of the gas-mixture.
In the case of a binary gas-mixture with convertible components,
the components will have the same potential, which may be denoted
by fjL, and the fundamental equation will be
p = a1L1t ** e °lt +a2L2t °* e "** , (342)
where Zj = e "* , L2 = e °* . (343)
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 183
From this equation, by differentiation and comparison with (98), we
obtain /*-.
v
(344)
ft-Bl £3 n-S-t
*6°**. (345)
From the general equation (93) with the preceding equations the
following is easily obtained, —
ieait +L2(c2t+E2)ta*e **' . (346)
v
We may obtain the relation between p, t, v, and m by eliminating
fi from (342) and (345). For this purpose we may proceed as follows.
From (342) and (345) we obtain
(347)
°* * (348)
and from these equations we obtain
- «2 * - «2 log 01 -p = («i - a,) log (a! - a2)
rr _
-I- aj log Zj - a2 log Z/2 + (A - c2 + aj — a2) log * - - ^ — -. (349)
(In the particular case when ax = 2a2 this equation will be equivalent
to (333).) By (347) and (348) we may easily eliminate JUL from (346).
The reader will observe that the relations thus deduced from the
fundamental equation (342) without any reference to the different
components of the gaseous mass are equivalent to those which relate
to the phases of dissipated energy of a binary gas-mixture with
components which are equivalent in substance but not convertible,
except that the equations derived from (342) do not give the quantities
of the proximate components, but relate solely to those properties
which are capable of direct experimental verification without the aid
of any theory of the constitution of the gaseous mass.
The practical application of these equations is rendered more simple
by the fact that the ratio 04 : a2 will always bear a simple relation to
unity. When a^ and a2 are equal, if we write a for their common
value, we shall have by (342) and (345)
pv = ami, (350)
184 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES,
and by (345) and (346)
e (3 .
a at
e
By this equation we may calculate directly the amount of heat
required to raise a given quantity of the gas from one given tem-
perature to another at constant volume. The equation shows that
the amount of heat will be independent of the volume of the gas.
The heat necessary to produce a given change of temperature in
the gas at constant pressure, may be found by taking the difference
of the values of x> as defined by equation (89), for the initial and final
states of the gas. From (89), (350), and (351) we obtain
" e ,
m z-i 1-2
r T , a at
Li+Lzt e
By differentiation of the two last equations we may obtain directly the
specific heats of the gas at constant volume and at constant pressure.
The fundamental equation of an ideal ternary gas-mixture with a
single relation of convertibility between its components is
i On Oi£
t e
u.2- .£2
4 /oeo\
(ooo)
where \ and X2 have the same meaning as on page 168.
* The Conditions of Internal and External Equilibrium for Solids
in contact with Fluids with regard to all possible States of
Strain of the Solids.
In treating of the physical properties of a solid, it is necessary to
consider its state of strain. A body is said to be strained when the
relative position of its parts is altered, and by its state of strain is
meant its state in respect to the relative position of its parts. We
have hitherto considered the equilibrium of solids only in the case in
which their state of strain is determined by pressures having the
same values in all directions about any point. Let us now consider
the subject without this limitation.
If x', 2/', z' are the rectangular co-ordinates of a point of a solid
body in any completely determined state of strain, which we shall call
*[This paper was originally printed in two parts, divided at this point. For dates see
heading, p. 55.]
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 185
the state of reference, and x, y, 0, the rectangular co-ordinates of the
same point of the body in the state in which its properties are the
subject of discussion, we may regard x, y, z as functions of x', y', z ',
the form of the functions determining the second state of strain. For
brevity, we may sometimes distinguish the variable state, to which
x, y, z relate, and the constant state (state of reference) to which
x', y', z' relate, as the strained and unstrained states ; but it must be
remembered that these terms have reference merely to the change of
form or strain determined by the functions which express the relations
of xy y, z and x', y', z', and do not imply any particular physical
properties in either of the two states, nor prevent their possible coin-
cidence. The axes to which the co-ordinates x, y, z and x', y', z' relate
will be distinguished as the axes of X, Y, Z and X', Y', Z'. It is not
necessary, nor always convenient, to regard these systems of axes as
identical, but they should be similar, i.e., capable of superposition.
The state of strain of any element of the body is determined by the
values of the differential coefficients of x, y, and z with respect to
x', y', and z' ; for changes in the values of x, y, z, when the differential
coefficients remain the same, only cause motions of translation of the
body. When the differential coefficients of the first order do not
vary sensibly except for distances greater than the radius of sensible
molecular action, we may regard them as completely determining the
state of strain of any element. There are nine of these differential
coefficients, viz.,
dx dx dx
dx~" djj" dz7'
dy dy dy
dx" dy" dz"
dz dz dz
dx" dy" dz7'
(354)
It will be observed that these quantities determine the orientation of
the element as well as its strain, and both these particulars must be
given in order to determine the nine differential coefficients. There-
fore, since the orientation is capable of three independent variations,
which do not affect the strain, the strain of the element, considered
without regard to directions in space, must be capable of six inde-
pendent variations.
The physical state of any given element of a solid in any unvarying
state of strain is capable of one variation, which is produced by
addition or subtraction of heat. If we write ey and rjy, for the energy
and entropy of the element divided by its volume in the state of
reference, we shall have for any constant state of strain
06y =
186 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
But if the strain varies, we may consider ev/ as a function of qv, an(i
the nine quantities in (354), and may write
(355)
where ZX', ... Zy denote the differential coefficients of eV' taken with
doc dz
respect to -^—n...^—f. The physical signification of these quantities
aX Q/Z
will be apparent, if we apply the formula to an element which in the
state of reference is a right parallelepiped having the edges dx', dy', dz',
and suppose that in the strained state the face in which x' has the
smaller constant value remains fixed, while the opposite face is moved
parallel to the axis of X. If we also suppose no heat to be imparted
to the element, we shall have, on multiplying by dxf dy' dz',
Now the first member of this equation evidently represents the work
done upon the element by the surrounding elements; the second
member must therefore have the same value. Since we must regard
the forces acting on opposite faces of the elementary parallelepiped as
equal and opposite, the whole work done will be zero except for the
dx
face which moves parallel to X. And since S-T—,dx' represents the
distance moved by this face, X^dy' dz' must be equal to the com-
ponent parallel to X of the force acting upon this face. In general,
therefore, if by the positive side of a surface for which xf is constant
we understand the side on which xf has the greater value, we may say
that Zx/ denotes the component parallel to X of the force exerted by
the matter on the positive side of a surface for which x' is constant
upon the matter on the negative side of that surface per unit of the
surface measured in the state of reference. The same may be said,
mutatis mutandis, of the other symbols of the same type.
It will be convenient to use 2 and 2' to denote summation with
respect to quantities relating to the axes X, Y, Z, and to the axes
X', Y', Zf, respectively. With this understanding we may write
This is the complete value of the variation of eV' for a given element
of the solid. If we multiply by dx' dy' dz', and take the integral for
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 187
the whole body, we shall obtain the value of the variation of the total
energy of the body, when this is supposed invariable in substance.
But if we suppose the body to be increased or diminished in substance
at its surface (the increment being continuous in nature and state
with the part of the body to which it is joined), to obtain the com-
plete value of the variation of the energy of the body, we must add
the integral
in which Ds' denotes an element of the surface measured in the state
of reference, and 8N' the change in position of this surface (due to
the substance added or taken away) measured normally and outward
in the state of reference. The complete value of the variation of the
intrinsic energy of the solid is therefore
ffft ^'dx'dy'dz' +fff^'x^)dxdy'dzf +f€v,SN'Ds'. (357)
This is entirely independent of any supposition in regard to the
homogeneity of the solid.
To obtain the conditions of equilibrium for solid and fluid masses
in contact, we should make the variation of the energy of the whole
equal to or greater than zero. But since we have already examined
the conditions of equilibrium for fluids, we need here only seek the
conditions of equilibrium for the interior of a solid mass and for the
surfaces where it comes in contact with fluids. For this it will be
necessary to consider the variations of the energy of the fluids only
so far as they are immediately connected with the changes in the
solid. We may suppose the solid with so much of the fluid as is in
close proximity to it to be enclosed in a fixed envelop, which is
impermeable to matter and to heat, and to which the solid is firmly
attached wherever they meet. We may also suppose that in the
narrow space or spaces between the solid and the envelop, which are
filled with fluid, there is no motion of matter or transmission of heat
across any surfaces which can be generated by moving normals to the
surface of the solid, since the terms in the condition of equilibrium
relating to such processes may be cancelled on account of the internal
equilibrium of the fluids. It will be observed that this method is
perfectly applicable to the case in which a fluid mass is entirely
enclosed in a solid. A detached portion of the envelop will then be
necessary to separate the great mass of the fluid from the small
portion adjacent to the solid, which alone we have to consider. Now
the variation of the energy of the fluid mass will be, by equation (13),
f*t SDn-f*p cSDv+Sj/Vi SDmlt (358)
where yF denotes an integration extending over all the elements of
188 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
the fluid (within the envelop), and 2X denotes a summation with
regard to those independently variable components of the fluid of
which the solid is composed. Where the solid does not consist of
substances which are components, actual or possible (see page 64),
of the fluid, this term is of course to be cancelled.
If we wish to take account of gravity, we may suppose that it acts
in the negative direction of the axis of Z. It is evident that the
variation of the energy due to gravity for the whole mass considered
is simply
fffgT'te dx'dy'dz', (359)
where g denotes the force of gravity, and I" the density of the
element in the state of reference, and the triple integration, as before,
extends throughout the solid.
We have, then, for the general condition of equilibrium,
ffft Sr]v,dx' dy'dz +fffW'xx, S dx'dy'dz'
fFp SDv+ 2lt/Vi SDm^ ^ 0. (360)
The equations of condition to which these variations are subject are :
(1) that which expresses the constancy of the total entropy,
fffSthrdafdtfdsf+fifr SN'Ds'+fF SDri = 0 ; (361)
(2) that which expresses how the value of SDv for any element of
the fluid is determined by changes in the solid,
SDv=-(aSx+/3Sy + -ySz)Ds-vv,SN'Ds', ' (362)
where a, /3, y denote the direction cosines of the normal to the
surface of the body in the state to which x, y, z relate, Ds the element
of the surface in this state corresponding to Ds' in the state of
reference, and v v/ the volume of an element of the solid divided by
its volume in the state of reference ;
(3) those which express how the values of SDml} SDm2, etc. for
any element in the fluid are determined by the changes in the solid,
SDm2 = - T^N'Ds', (363)
etc.,
where I\', IV, etc. denote the separate densities of the several com-
ponents in the solid in the state of reference.
Now, since the variations of entropy are independent of all the
other variations, the condition of equilibrium (360), considered with
regard to the equation of condition (361), evidently requires that
throughout the whole system
t = const. (364)
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 189
We may therefore use (361) to eliminate the fourth and fifth integrals
from (360). If we multiply (362) by p, and take the integrals for
the whole surface of the solid and for the fluid in contact with it, we
obtain the equation
f*p 8Dv = -fp(a8x+/3Sy + ySz)D8-fpvv, WDa', (365)
by means of which we may eliminate the sixth integral from (360).
If we add equations (363) multiplied respectively by yu1? yu2, etc.,
and take the integrals, we obtain the equation
(366)
by means of which we may eliminate the last integral from (360).
The condition of equilibrium is thus reduced to the form
+f€v,8N'Ds'-ftnv,SN'Ds'+fp(a8x+/3Sy+7Sz)Ds
0, (367)
in which the variations are independent of the equations of condition,
and in which the only quantities relating to the fluids are p and fa ,
/*2> etc-
Now by the ordinary method of the calculus of variations, if we
write a, ft', y for the direction- cosines of the normal to the surface
of the solid in the state of reference, we have
X* Sx Ds' -fff^-j. Sxdx'dy'dz', (368)
with similar expressions for the other parts into which the first
integral in (367) may be divided. The condition of equilibrium is
thus reduced to the form
8'^0. (369)
It must be observed that if the solid mass is not continuous
throughout in nature and state, the surface-integral in (368), and
therefore the first surface-integral in (369), must be taken to apply
not only to the external surface of the solid, but also to every surface
of discontinuity within it, and that with reference to each of the
two masses separated by the surface. To satisfy the condition of
190 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
equilibrium, as thus understood, it is necessary and sufficient that
throughout the solid mass
ISf(2jjZto)-grto-0; (370)
that throughout the surfaces where the solid meets the fluid
JV2ZV^x'to)+#*l>2(a&0 = 0, (371)
and [«v'-fyv'+l>iV-210£iri')] SN'^0 ; (372)
and that throughout the internal surfaces of discontinuity
where the suffixed numerals distinguish the expressions relating to
the masses on opposite sides of a surface of discontinuity.
Equation (370) expresses the mechanical conditions of internal
equilibrium for a continuous solid under the influence of gravity. If
we expand the first term, and set the coefficients of Sx, Sy, and Sz
separately equal to zero, we obtain
(374)
dXz>_
' ~ ' ~ '
dx' ~ dy' ~ dz
x, dYT dYz,_
~ '
dx dy dz
dZ,
dx' dy' dz'
The first member of any one of these equations multiplied by dw'dy'dz'
evidently represents the sum of the components parallel to one of the
axes X, F, Z of the forces exerted on the six faces of the element
dx'dy'dz' by the neighboring elements.
As the state which we have called the state of reference is arbitrary,
it may be convenient for some purposes to make it coincide with the
state to which x, y, z relate, and the axes X', F, Z with the axes
X, F, Z. The values of X %>,... Zz> on this particular supposition
may be represented by the symbols Xx, ... Zz. Since
j
dx'
and since, when the states, x, y, z and x' y' z coincide, and the axes
dx d\i
X, F, Z, and X', F", Z', d-^—, and d-^-, represent displacements which
differ only by a rotation, we must have
*r=FX) (375)
and for similar reasons,
Yz = ZY, ZX = X2. (376)
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 191
The six quantities Zx, FY, Zz, ZY or Fx, Yz or Z?, and Zx or Xz are
called the rectangular components of stress, the three first being
the longitudinal stresses and the three last the shearing stresses. The
mechanical conditions of internal equilibrium for a solid under the
influence of gravity may therefore be expressed by the equations
dX?
dx dy dz
dx dy dz
dZ?
dx dy dz
(377)
where T denotes the density of the element to which the other
symbols relate. Equations (375), (376) are rather to be regarded as
expressing necessary relations (when XX,...ZZ are regarded as
internal forces determined by the state of strain of the solid) than
as expressing conditions of equilibrium. They will hold true of a
solid which is not in equilibrium, — of one, for example, through which
vibrations are propagated, — which is not the case with equations (377).
Equation (373) expresses the mechanical conditions of equilibrium
for a surface of discontinuity within the solid. If we set the coefficients
of Sx, Sy, Sz, separately equal to zero we obtain
(378)
Now when the a, {?, y represent the direction-cosines of the normal
in the state of reference on the positive side of any surface within the
solid, an expression of the form
a'Xv + pXT + yXv (379)
represents the component parallel to X of the force exerted upon
the surface in the strained state by the matter on the positive side
per unit of area measured in the state of reference. This is evident
from the consideration that in estimating the force upon any surface
we may substitute for the given surface a broken one consisting
of elements for each of which either x' or y' or zf is constant. Applied
to a surface bounding a solid, or any portion of a solid which may
not be continuous with the rest, when the normal is drawn outward
as usual, the same expression taken negatively represents the com-
ponent parallel to X of the force exerted upon the surface (per
unit of surface measured in the state of reference) by the interior
of the solid, or of the portion considered. Equations (378) therefore
express the condition that the force exerted upon the surface of
192 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
discontinuity by the matter on one side and determined by its state
of strain shall be equal and opposite to that exerted by the matter
on the other side. Since
we may also write
a (^x')i + P(*T\ + y'(X*\ = a'(*x<)2 + P(Xv\ + v'(*z')2 >\ (380)
etc., J
where the signs of a', /$', y may be determined by the normal on
either side of the surface of discontinuity.
Equation (371) expresses the mechanical condition of equilibrium
for a surface where the solid meets a fluid. It involves the separate
equations
Ds (381)
Ds
the fraction -=p denoting the ratio of the areas of the same element
of the surface in the strained and unstrained states of the solid.
These equations evidently express that the force exerted by the
interior of the solid upon an element of its surface, and determined
by the strain of the solid, must be normal to the surface and equal
(but acting in the opposite direction) to the pressure exerted by the
fluid upon the same element of surface.
If we wish to replace a and Ds by a', P, y', and the quantities
which express the strain of the element, we may make use of the
following considerations. The product aDs is the projection of the
Ds
element Ds on the Y-Z plane. Now since the ratio jr-f is independent
of the form of the element, we may suppose that it has any convenient
form. Let it be bounded by the three surfaces x' = const., y' = const.,
z' = const., and let the parts of each of these surfaces included by the
two others with the surface of the body be denoted by L, M, and N, or
by L', M', and N', according as we have reference to the strained or
unstrained state of the body. The areas of L', M', and N' are evidently
a'Ds', B'Ds', and y'Ds' ; and the sum of the projections of Z, Mt and
N upon any plane is equal to the projection of Ds upon that plane,
since L, M, and N with Ds include a solid figure. (In propositions of
this kind the sides of surfaces must be distinguished. If the normal
to Ds falls outward from the small solid figure, the normals to L, M,
and N must fall inward, and vice versa.) Now L' is a right-angled
triangle of which the perpendicular sides may be called dy' and dzf.
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 193
The projection of L on the Y-Z plane will be a triangle, the angular
points of which are determined by the co-ordinates
dy j, . dz , ,
y, z; y,
the area of such a triangle is
_ __ , , , ,
dy'dzf dy'dz~'ry(
or, since J dyr dz represents the area of L',
(dy dz__dz dy\ , n ,
\dy' dz' dy' dz')a
(That this expression has the proper sign will appear if we suppose
for the moment that the strain vanishes.) The areas of the projections
of M and N upon the same plane will be obtained by changing yf, z'
and a' in this^expression into 2', x', and /3', and into x', y', and y. The
sum of the three) expressions may be substituted for a Ds in (381).
We shall hereafter use S' to denote the sum of the three terms
obtained by rotary substitutions of quantities relating to the axes
X', Y', Z' (i.e., by changing x'y y', z' into y', z', x', and into /, x', yr,
with similar changes in regard to a', fl', y ', and other quantities
relating to these axes), and 2 to denote the sum of the three terms
obtained by similar rotary changes of quantities relating to the axes
X, Y, Z. This is only an extension of our previous use of these
symbols.
With this understanding, equations (381) may be reduced to the
form
Yc^2/ dz dz dy\\_
a --- °
(382)
etc.
The formula (372) expresses the additional condition of equilibrium
which relates to the dissolving of the solid, or its growth without
discontinuity. If the solid consists entirely of substances which are
actual components of the fluid, and there are no passive resistances
which impede the formation or dissolving of the solid, SN' may have
either positive or negative values, and we must have
€v — tffr, —pvv, = Sj ( ywJV). (383)
But if some of the components of the solid are only possible com-
ponents (see page 64) of the fluid, SN' is incapable of positive values,
as the quantity of the solid cannot be increased, and it is sufficient
for equilibrium that
ev, _ tlfr +pv, ^ 2/^iy). (384)
To express- condition (383) in a form independent of the state of
reference, we may use ev> ^v* I\, etc., to denote the densities of
G.I. N
194 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
energy, of entropy, and of the several component substances in the
variable state of the solid. We shall obtain, on dividing the equation
by vv,,
ev-^v+^ = 2:i(^iri). (385)
It will be remembered that the summation relates to the several
components of the solid. If the solid is of uniform composition
throughout, or if we only care to consider the contact of the solid
and the fluid at a single point, we may treat the solid as composed of
a single substance. If we use fa to denote the potential for this
substance in the fluid, and T to denote the density of the solid in the
variable state (I", as before denoting its density in the state of
reference), we shall have
€T-t^+pvT = juiirt (386)
and ev — tijv +p = faT. (387)
To fix our ideas in discussing this condition, let us apply it to the
case of a solid body which is homogeneous in nature and in state of
strain. If we denote by e, TJ, v, and ra, its energy, entropy, volume,
and mass, we have
€ — tij +pv = fam. (388)
Now the mechanical conditions of equilibrium for the surface where
a solid meets a fluid require that the traction upon the surface deter-
mined by the state of strain of the solid shall be normal to the surface.
This condition is always satisfied with respect to three surfaces at
right angles to one another. In proving this well-known proposition,
we shall lose nothing in generality, if we make the state of 'reference,
which is arbitrary, coincident with the state under discussion, the
axes to which these states are referred being also coincident. We
shall then have, for the normal component of the traction per unit
of surface across any surface for which the direction-cosines of the
normal are a, /3, y (compare (379), and for the notation Xx, etc.,
page 190),
or, by (375), (376),
(389)
We may also choose any convenient directions for the co-ordinate
axes. Let us suppose that the direction of the axis of X is so chosen
that the value of S for the surface perpendicular to this axis is as
great as for any other surface, and that the direction of the axis of Y
(supposed at right angles to X) is such that the value of S for the
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 195
surface perpendicular to it is as great as for any other surface
passing through the axis of X. Then, if we write -*— , -T^, ~j~ f°r
the differential coefficients derived from the last equation by treating
a, ft, and y as independent variables,
dS
, , jfi.j
-T- da + -S-Q dB + -7- dy - 0,
act a/5 ay
when
and a = l, 0 = 0, y = 0.
mi_ j. • ~ j ~
That is, -7^ == 0, and -,- = 0,
when a = l, 0 = 0, y = 0.
Hence ^Y = 0, and ZX = Q. (390)
Moreover, -^-5 cZ/3 4- -j- dy = 0,
ctp ay
when a = 0, da = 0,
and 0 = 1, y = 0.
Hence Fz = 0. (391)
Therefore, when the co-ordinate axes have the supposed directions,
which are called the principal axes of stress, the rectangular com-
ponents of the traction across any surface (a, /3, y) are by (379)
aXx, /3FY, 7ZZ. (392)
Hence, the traction across any surface will be normal to that
surface, —
(1), when the surface is perpendicular to a principal axis of stress ;
(2), if two of the principal tractions Xx, FY, Zz are equal, when
the surface is perpendicular to the plane containing the two corre-
sponding axes (in this case the traction across any such surface is
equal to the common value of the two principal tractions) ;
(3), if the principal tractions are all equal, the traction is normal
and constant for all surfaces.
It will be observed that in the second and third cases the positions
of the principal axes of stress are partially or wholly indeterminate
(so that these cases may be regarded as included in the first), but the
values of the principal tractions are always determinate, although not
always different.
If, therefore, a solid which is homogeneous in nature and in state of
strain is bounded by six surfaces perpendicular to the principal axes
of stress, the mechanical conditions of equilibrium for these surfaces
may be satisfied by the contact of fluids having the proper pressures
196 EQUILIBKTUM OF HETEROGENEOUS SUBSTANCES.
(see (381)), which will in general be different for the different pairs of
opposite sides, and may be denoted by p', p", p'". (These pressures
are equal to the principal tractions of the solid taken negatively.)
It will then be necessary for equilibrium with respect to the tendency
of the solid to dissolve that the potential for the substance of the
solid in the fluids shall have values /*/, /*/', ///", determined by the
equations
e-tq+p'v =yu/m, (393)
e-tri +p"v = /jLi'm, (394)
e-tr}+p"fv = fj.i"m. (395)
These values, it will be observed, are entirely determined by the
nature and state of the solid, and their differences are equal to
the differences of the corresponding pressures divided by the density
of the solid.
It may be interesting to compare one of these potentials, as /*/,
with the potential (for the same substance) in a fluid of the same
temperature t and pressure p' which would be in equilibrium with the
same solid subjected on all sides to the uniform pressure p'. If we
write [e]y, [77]^, [v]^, and [/ujy for the values which e, r\y v, and fa
would receive on this supposition, we shall have
[*k-*W*+p'^=M*™- (396>
Subtracting this from (393), we obtain
€ - [£]P' -ty + t [r{\p, +p'v -p' [v]j, = fam - [fi^m. (397)
4
Now it follows immediately from the definitions of energy and
entropy that the first four terms of this equation represent the work
spent upon the solid in bringing it from the state of hydrostatic stress
to the other state without change of temperature, and p'v— p'\v\p>
evidently denotes the work done in displacing a fluid of pressure p'
surrounding the solid during the operation. Therefore, the first
number of the equation represents the total work done in bringing
the solid when surrounded by a fluid of pressure p' from the state
of hydrostatic stress pr to the state of stress p', p", p"f. This quantity
is necessarily positive, except of course in the limiting case when
p'=zp"=p'". If the quantity of matter of the solid body be unity,
the increase of the potential in the fluid on the side of the solid on
which the pressure remains constant, which will be necessary to
maintain equilibrium, is equal to the work done as above described.
Hence, /// is greater than [//J^/, and for similar reasons p" is greater
than the value of the potential which would be necessary for equili-
brium if the solid were subjected to the uniform pressure p", and
///" greater than that which would be necessary for equilibrium if
the solid were subjected to the uniform pressure p'". That is (if we
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 197
adapt our language to what we may regard as the most general case,
viz., that in which the fluids contain the substance of the solid but
are not wholly composed of that substance), the fluids in equilibrium
with the solid are all supersaturated with respect to the substance
of the solid, except when the solid is in a state of hydrostatic stress ;
so that if there were present in any one of these fluids any small frag-
ment of the same kind of solid subject to the hydrostatic pressure of
the fluid, such a fragment would tend to increase. Even when no
such fragment is present, although there must be perfect equilibrium
so far as concerns the tendency of the solid to dissolve or to increase
by the accretion of similarly strained matter, yet the presence of the
solid which is subject to the distorting stresses, will doubtless facilitate
the commencement of the formation of a solid of hydrostatic stress
upon its surface, to the same extent, perhaps, in the case of an
amorphous body, as if it were itself subject only to hydrostatic
stress. This may sometimes, or perhaps generally, make it a necessary
condition of equilibrium in cases of contact between a fluid and an
amorphous solid which can be formed out of it, that the solid at the
surface where it meets the fluid shall be sensibly in a state of hydro-
static stress.
But in the case of a solid of continuous crystalline structure, sub-
jected to distorting stresses and in contact with solutions satisfying
the conditions deduced above, although crystals of hydrostatic stress
would doubtless commence to form upon its surface (if the distorting
stresses and consequent supersaturation of the fluid should be carried
too far), before they would commence to be formed within the fluid
or on the surface of most other bodies, yet within certain limits the
relations expressed by equations (393)-(395) must admit of realization,
especially when the solutions are such as can be easily supersaturated.*
It may be interesting to compare the variations of p, the pressure
in the fluid which determines in part the stresses and the state of
strain of the solid, with other variations of the stresses or strains in
the solid, with respect to the relation expressed by equation (388).
To examine this point with complete generality, we may proceed in
the following manner.
Let us consider so much of the solid as has in the state of reference
the form of a cube, the edges of which are equal to unity, and
parallel to the co-ordinate axes. We may suppose this body to be
homogeneous in nature and in state of strain both in its state of
*Tbe effect of distorting stresses in a solid on the phenomena of crystallization and
liquefaction, as well as the effect of change of hydrostatic pressure common to the
solid and liquid, was first described by Professor James Thomson. See Trans. R. S.
Edin., vol. xvi, p. 575; and Proc. Roy. Soc., vol. xi, p. 473, or Phil. Mag., ser. 4, vol.
xxiv, p. 395.
198 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
reference and in its variable state. (This involves no loss of generality,
since we may make the unit of length as small as we choose.) Let
the fluid meet the solid on one or both of the surfaces for which Z'
is constant. We may suppose these surfaces to remain perpendicular
to the axis of Z in the variable state of the solid, and the edges in
which y' and z' are both constant to remain parallel to the axis of X.
It will be observed that these suppositions only fix the position of
the strained body relatively to the co-ordinate axes, and do not in
any way limit its state of strain.
It follows from the suppositions which we have made that
dz _ dz _ dy
-T-, = const. = 0, -j—, — const. = 0, -^ = const. = 0 ; (398)
and ZF=0, Fz. = 0, Zz,= -p^jjt. -, (399)
Hence, by (355),
dx 7
dff. (400)
Again, by (388),
de = tdr] + T]dt—pdv — vdp+mdjUL1. (401)
Now the suppositions which have been made require that
dx dy dz
V=M$M> <402>
, 7 dy dz -.dx , dz dx 7dy , dx dy 7dz < ,..
and dv = -f-, -,— -, d j-t -f •T-f -T-? d -—, -f -T-, -^-f d-r-, . (403)
dy dz dx dz dx dy dx dy dz
Combining equations (400), (401), and (403), and observing that
€v, and r)y, are equivalent to e and TJ, we obtain
dy dz\ -.dx , ^ -.dx , /T, dz dx\ 7dy
The reader will observe that when the solid is subjected on all sides
to the uniform normal pressure p, the coefficients of the differentials
in the second member of this equation will vanish. For the expression
-p> -7-7 represents the projection on the Y-Z plane of a side of the
parallelepiped for which xr is constant, and multiplied by p it will
be equal to the component parallel to the axis of X of the total
pressure across this side, i.e., it will be equal to Xx> taken negatively.
The case is similar with respect to the coefficient of d-p,; and X?,
evidently denotes a force tangential to the surface on which it acts.
EQUILIBKIUM OF HETEROGENEOUS SUBSTANCES. 199
It will also be observed, that if we regard the forces acting upon
the sides of the solid parallelepiped as composed of the hydrostatic
pressure p together with additional forces, the work done in any infini-
tesimal variation of the state of strain of the solid by these additional
forces will be represented by the second member of the equation.
We will first consider the case in which the fluid is identical in
substance with the solid. We have then, by equation (97), for a mass
of the fluid equal to that of the solid,
q9dt—Vydp+mdfil*aO, (405)
T)F and VF denoting the entropy and volume of the fluid. By sub-
traction we obtain
dy dz\-.dx v ,dx (^ dz dx\^dy /Ai\a\
d+x*d+*+* d" (406)
( I JT dx dii
Now if the quantities -v->, -,— ,, -A remain constant, we shall have
for the relation be^veen the variations of temperature and pressure
which is necessary for the preservation of equilibrium
dp t]F-r} Q
where Q denotes the heat which would be absorbed if the solid body
should pass into the fluid state without change of temperature or
pressure. This equation is similar to (131), which applies to bodies
subject to hydrostatic pressure. But the value of -y- will not gener-
ally be the same as if the solid were subject on all sides to the uni-
form normal pressure p ; for the quantities v and r\ (and therefore
Q) will in general have different values. But when the pressures on
all sides are normal and equal, the value of T- will be the same,
whether we consider the pressure when varied as still normal and
doc doc di/
equal on all sides, or consider the quantities -7— „ -v->, ~A as constant.
But if we wish to know how the temperature is affected if the pres-
sure between the solid and fluid remains constant, but the strain of
the solid is varied in any way consistent with this supposition, the
differential coefficients of t with respect to the quantities which
express the strain are indicated by equation (406). These differential
coefficients all vanish, when the pressures on all sides are normal
and equal, but the differential coefficient -7-, when -j—,, -^—., J are
dp dx dy dy
200 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
constant, or when the pressures on all sides are normal and equal,
vanishes only when the density of the fluid is equal to that of the
solid.
The case is nearly the same when the fluid is not identical in
substance with the solid, if we suppose the composition* of the fluid to
remain unchanged. We have necessarily with respect to the fluid
flu \<F>
dt+W dp* (408)
dt/p,m \dpJtt
where the index (F) is used to indicate that the expression to which
it is affixed relates to the fluid. But by equation (92)
F)
i -TV r/ \:j — ) » -j
\ at /Pt m \dml/tl Pim \dp/t,m lt Pt m
Substituting these values in the preceding equation, transposing
terms, and multiplying by m, we obtain
dp+mdu^O. (410)
.m ' j '
By subtracting this equation from (404) we may obtainfan equation
similar to (406), except that in place of rjf and VF we shall have the
expressions
dv VF)
The discussion of equation (406) will therefore apply mutatis Mutandis
to this case.
We may also wish to find the variations in the composition of the
fluid which will be necessary for equilibrium when the pressure p or
.... dx dx dy . , .,
the quantities T— „ -T-?, -grp are varied, the temperature remaining
constant. If we know the value for the fluid of the quantity repre-
sented by f on page 87 in terms of t, p, and the quantities of the
several components m^ m2, m3, etc., the first of which relates to the
substance of which the solid is formed, we can easily find the value
of //! in terms of the same variables. Now in considering variations
in the composition of the fluid, it will be sufficient if we make all but
one of the components variable. We may therefore give to rml
constant value, and making t also constant, we shall have
o-fetc.
* A suffixed m stands here, as elsewhere in this paper, for all the symbols mlt m.2, etc.,
except such as may occur in the differential coefficient.
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 201
Substituting this value in equation (404), and cancelling the term
containing dt, we obtain
du,\(¥) i f v dy dz\ ^dx
-j) dm»+etc. = (Xx>+p-jZ-, -j-Adj—,
dm3/tip,m ^ dy dz/ dx
(411)
This equation shows the variation in the quantity of any one of the
components of the fluid (other than the substance which forms the
solid) which will balance a variation of p. or of -^—ft -,— ,, -r^,, with
dx dy dy
respect to the tendency of the solid to dissolve.
Fundamental Equations for Solids.
The principles developed in the preceding pages show that the
solution of problems relating to the equilibrium of a solid, or at least
their reduction to purely analytical processes, may be made to depend
upon our knowledge of the composition and density of the solid at
every point in some particular state, which we have called the state
of reference, and of the relation existing between the quantities which
. i , i d/x ctoG az , f i /
have been represented by eV'> ?7v'> j~>» j— /> • - • • ~j~. '<* %> y> and z.
When the solid is in contact with fluids, a certain knowledge of the
properties of the fluids is also requisite, but only such as is necessary
for the solution of problems relating to the equilibrium of fluids
among themselves.
If in any state of which a solid is capable, it is homogeneous in its
nature and in its state of strain, we may choose this state as the state
of reference, and the relation between eV'> flv> -T~/» • • • T-/> will be
dx dz
independent of a?7, y', z'. But it is not always possible, even in the
case of bodies which are homogeneous in nature, to bring all the
elements simultaneously into the same state of strain. It would not
be possible, for example, in the case of a Prince Rupert's drop.
If, however, we know the relation between eV', flv'> ;/""•• -T""
for any kind of homogeneous solid, with respect to any given state of
reference, we may derive from it a similar relation with respect to
any other state as a state of reference. For if x', y', z* denote the
co-ordinates of points of the solid in the first state of reference, and
202
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
x", y", z" the co-ordinates of the same points in the second state of
reference, we shall have necessarily
dx dx dx" . dx dy" , dx dz"
'
dx"
dx"
dx"
dx'
dy',,
dz'
dy"
dx'
dz"
dx'
dy'
dz"
dz'
dz"
dy'
dz'
and if we write R for the volume of an element in the state (x", y", z")
divided by its volume in the state (x'} y', z'\ we shall have
(413)
. (414)
If, then, we have ascertained by experiment the value of ev> in terms
of J/V'> -T-, >> - • • -T-?J and the quantities which express the composition
of the body, by the substitution of the values given in (412)-(414),
,,,,,. . £ dx dz dx" dz" , .
we shall obtain ev» m terms of ^v«, -7-77, . . . -^-7,, -j-r, . . . ^-^-, and the
dx dz dx dz
quantities which express the composition of the body.
We may apply this to the elements of a body which may be
variable from point to point in composition and state of strain in a
given state of reference (x", y", z"), and if the body is fully described
in that state of reference, both in respect to its composition and to the
displacement which it would be necessary to give to a homogeneous
solid of the same composition, for which ev is known in terms of T/F,
dx dz
-7-7, . . . -j—ft and the quantities which express its composition, to
bring it from the state of reference (x'} y', z) into a similar and
similarly situated state of strain with that of the element of the non-
dx" dz"
homogeneous body, we may evidently regard -7-7 , . . . -r-r
as known
for each element of the body, that is, as known in terms of x", y", z".
dir el z
We shall then have ev» in terms of ;/v», -7-7,, . . . -7-77, x", y", z" ; and
since the composition of the body is known in terms of x", y", z", and
the density, if not given directly, can be determined from the density
of the homogeneous body in its state of reference (x', y', z'), this is
sufficient for determining the equilibrium of any given state of the
non-homogeneous solid.
An equation, therefore, which expresses for any kind of solid, and
with reference to any determined state of reference, the relation
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 203
between the quantities denoted by ev/, fly, T-->, . . . -T-?, involving also
the quantities which express the composition of the body, when that
is capable of continuous variation, or any other equation from which
the same relations may be deduced, may be called a fundamental
equation for that kind of solid. It will be observed that the sense in
which this term is here used, is entirely analogous to that in which we
have already applied the term to fluids and solids which are subject
only to hydrostatic pressure.
When the fundamental equation between eV'> ^7v> -j-, >•> • • • j~? is
known, we may obtain by differentiation the values of t, Xx>, . . . Zv
in terms of the former quantities, which will give eleven independent
relations between the twenty-one quantities
dx dz v „
€y/' ^v/> dx" ' ' ' dz" x/' ' ' ' z'} (415)
which are all that exist, since ten of these quantities are independent.
All these equations may also involve variables which express the
composition of the body, when that is capable of continuous variation.
If we use the symbol t/*v to denote the value of \js (as defined on
page 89) for any element of a solid divided by the volume of the
element in the state of reference, we shall have
\/rv, = ev,-^v,. (416,x
The equation (356) may be reduced to the form
x,6j;). (417)
Therefore, if we know the value of \fsv in terms of the variables t
(liCf (I Z
-j—,, . . . -T—,, together with those which express the composition of the
body, we may obtain by differentiation the values of rjv>, Xx>, . . . Zz,
in terms of the same variables. This will make eleven independent
relations between the same quantities as before, except that we shall
have \/rv. instead of ev>. Or if we eliminate \Jsv by means of equation
(416), we shall obtain eleven independent equations between the
quantities in (415) and those which express the composition of the
body. An equation, therefore, which determines the value of \/sv,
/Y/Y* ft ft
as a function of the quantities t, -*—„ . . . -1-7, and the quantities which
express the composition of the body when it is capable of continuous
variation, is a fundamental equation for the kind of solid to which it
relates.
In the discussion of the conditions of equilibrium of a solid, we
might have started with the principle that it is necessary and sufficient
204 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
for equilibrium that the temperature shall be uniform throughout the
whole mass in question, and that the variation of the force-function
(-i/r) of the same mass shall be null or negative for any variation in
the state of the mass not affecting its temperature. We might have
assumed that the value of \fs for any same element of the solid is a
function of the temperature and the state of strain, so that for
constant temperature we might write
the quantities XX', . . . Zz,, being defined by this equation. This
would be only a formal change in the definition of X^>, . . . Z% and
would not affect their values, for this equation holds true of JTX,, . . . Zz
as defined by equation (355). With such data, by transformations
similar to those which we have employed, we might obtain similar
results.* It is evident that the only difference in the equations would
be that i//v would take the place of eT, and that the terms relating to
entropy would be wanting. Such a method is evidently preferable
with respect to the directness with which the results are obtained.
The method of this paper shows more distinctly the rdle of energy and
entropy in the theory of equilibrium, and can be extended more
naturally to those dynamical problems in which motions take place
under the condition of constancy of entropy of the elements of
a solid (as when vibrations are propagated through a solid), just as
the other method can be more naturally extended to dynamical
problems in which the temperature is constant. (See ,note on
page 90.)
We have already had occasion to remark that the state of strain
of any element considered without reference to directions in space is
capable of only six independent variations. Hence, it must be possible
to express the state of strain of an element by six functions of
-T-7, . . . -j-,, which are independent of the position of the element.
Ct/OC Ct/2/
For these quantities we may choose the squares of the ratios of
elongation of lines parallel to the three co-ordinate axes in the state
of reference, and the products of the ratios of elongation for each
pair of these lines multiplied by the cosine of the angle which they
include in the variable state of the solid. If we denote these quantities
by A, B, C, a, 6, c we shall have
* For an example of this method, see Thomson and Tait's Natural Philosophy, vol. i,
p. 705. With regard to the general theory of elastic solids, compare also Thomson's
Memoir "On the Thermo-elastic and Thermo-magnetic Properties of Matter" in the
Quarterly Journal oj Mathematics, vol. i, p. 57 (1855), and Green's memoirs on the
propagation, reflection, and refraction of light in the Transactions of the Cambridge
Philosophical Society, vol. vii.
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 205
- <418>
The determination of the fundamental equation for a solid is thus
reduced to the determination of the relation between ev/, 7/V'> A, B, C,
a, b, c, or of the relation between \/^T, t, A, B, Cy a, b, c.
In the case of isotropic solids, the state of strain of an element, so
far as it can affect the relation of ev, and TJT) or of \fsv> and t, is capable
of only three independent variations. This appears most distinctly
as a consequence of the proposition that for any given strain of an
element there are three lines in the element which are at right angles
to one another both in its unstrained and in its strained state. If
the unstrained element is isotropic, the ratios of elongation for these
three lines must with IJT determine the value €v>, or with t determine
the value of \fsv>.
To demonstrate the existence of such lines, which are called the
principal axes of strain, and to find the relations of the elongations
fine dz
of such lines to the quantities -j—,, . . . -T-,, we may proceed as follows.
The ratio of elongation r of any line of which a', /3', y are the
direction-cosines in the state of reference is evidently given by the
equation
dx , dx ,dx A2
dz „, . dz
Now the proposition to be established is evidently equivalent to this
— that it is always possible to give such directions to the two systems
of rectangular axes X', Y', Z ', and X, Y, Z, that
(421)
^ _ _
dx' dx'~ ' dy'~
We may choose a line in the element for which the value of r is at
least as great as for any other, and make the axes of X and X' parallel
to this line in the strained and unstrained states respectively.
Then =° =
206 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
Moreover, if we write ; , , ^/v » 7 / for the differential coefficients
da dp dy
obtained from (420) by treating a, ft', y as independent variables,
when
and a'=l, /3' = 0, y' =
That is, '
when a' = l, /3' = 0, y' = 0.
Hence, ^ = 0, £ = 0. ,
Therefore a line of the element which in the unstrained state is per-
pendicular to X' is perpendicular to X in the strained state. Of all
such lines we may choose one for which the value of r is at least as
great as for any other, and make the axes of Y' and Y parallel to this
line in the unstrained and in the strained state respectively. Then
0; ' (424)
and it may easily be shown by reasoning similar to that which lias
just been employed that
Lines parallel to the axes of X', Y', and Z' in the unstrained body
will therefore be parallel to X, F, and Z in the strained body, and the
ratios of elongation for such lines will be
dx dy dz
dx" dy" US'
These lines have the common property of a stationary value of the
ratio of elongation for varying directions of the line. This appears
from the form to which the general value of r2 is reduced by the
positions of the co-ordinate axes, viz.,
Having thus proved the existence of lines, with reference to any
particular strain, which have the properties mentioned, let us
proceed to find the relations between the ratios of elongation
for these lines (the principal axes of strain) and the quantities
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 207
fi '/* ft %
-T-,,.» -j—, under the most general supposition with respect to the
dec dz
position of the co-ordinate axes.
For any principal axis of strain we have
'
da dp dy
when a da + /3' d/3' + y dy = 0,
the differential coefficients in the first of these equations being
determined from (420) as before. Therefore,
a' da' "P d/3' ~y dy' '
From (420) we obtain directly
Pd(r*) ,y'd(r*)_
"2 'd" ~2~d'
( ?
From the two last equations, in virtue of the necessary relation
a2+/S/2-hy/2=l, we obtain
(428)
j /-
or, if we substitute the values of the differential coefficients taken
from (420),
X \A/X \ . i »-. / CLX (A/X
a
a
a
dx
dx
Cjl/X CvZ :
x dx
dx
(429)
If we eliminate a', /^ y' from these equations, we may write the
result in the form,
(dx dx\
dx dx
„
'
dx\
2
= 0.
(430)
We may write
Then
(431)
(432)
208 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
Also*
ir»_y/ (?(dx\*/dx\*__y/dx_ dx\ (dx dx\\
x dx
dyf
dx
dz^^dx dx dy dy __dx dx dz dz\
dxf \dy') "'dx7 dy7 d^/~d^^d^'~d^ dot dy'}
(433)
dxr
--^ — V
/ '
This may also be written
dx' dy'
dy dy
(434)
dx' dy'
In the reduction of the value of G, it will be convenient to use the
symbol 2 to denote the sum of the six terms formed by changing
3+3
x, y, z, into y, z, x ; z,x,y, x, z, y ; y, x, z ; and z, y, x ; and the
symbol 2 in the same sense except that the last three terms are to
3-3
be taken negatively; also to use Z' in a similar sense with respect
3-3
to xf, y', zf ; and to use x', y', zf as equivalent to a?7, y', z', except that
they are not to be affected by the sign of summation. With this
understanding we may write
Gr=
3_3
dx
,,QfU
(4do)
\dy' dy'J " \dz' dz's
In expanding the product of the three sums, we may cancel on
account of the sign 2' the terms which do not contain all the three
3-3
expressions dx, dy, and dz. Hence we may write
/j__ y/ y (dx dx dy dy dz dz\
"3-33+3 \^x/ dx' dy' dy' dz dz')
~(dx dy dz ~,(dx dy dz\\
~ 3+3 \dx' dy' dz 3_3 \dx' dy' dz')}
y (dx dy dz\ ~, (dx dy dz\
~ z-z\dx' dyf dz') 3_3 \dx' dy' dz'/
(436)
* The values of F and G given in equations (434) and (438), which are here deduced
at length, may be derived from inspection of equation (430) by means of the usual
theorems relating to the multiplication of determinants. See Salmon's Lessons Intro-
ductory to the Modern Higher Algebra, 2d ed., Lesson III; or Baltzer's Theorie und
Anwendung der Determinanten, § 5.
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
209
Or, if we set
dx
dx
dx
dx'
dy
dy'
dy
dy'
dz
dy'
dz'
dy
dx'
dz
dx'
dz'
dz
dz7
(437)
we shall have
G = H*. (438)
It will be observed that F represents the sum of the squares of the
nine minors which can be formed from the determinant in (437), and
that E represents the sum of the squares of the nine constituents of
the same determinant.
Now we know by the theory of equations that equation (431) will
be satisfied in general by three different values of r2, which we may
denote by rf, r22, r32, and which must represent the squares of the
ratios of elongation for the three principal axes of strain; also that
E, F, G are symmetrical functions of rx2, r22, r32, viz.,
(439)
Hence, although it is possible to solve equation (431) by the use of
trigonometrical functions, it will be more simple to regard €T as a
function of JJT and the quantities E, F, G (or H), which we have
expressed in terms of -?-? , . . . -T-? . Since ev, is a single- valued function
of t]v and r^y r22, r32 (with respect to all the changes of which the
body is capable), and a symmetrical function with respect to 2
r
2,
r32, and since rx2, r22, r32 are collectively determined without ambiguity
by the values of E, F, and H, the quantity eV' must be a single- valued
function of j/V'> E, F, and H. The determination of the fundamental
equation for isotropic bodies is therefore reduced to the determination
of this function, or (as appears from similar considerations) the deter-
mination of i/rv, as a function of t, E, F, and H.
It appears from equations (439) that E represents the sum of the
squares of the ratios of elongation for the principal axes of strain,
that F represents the sum of the squares of the ratios of enlargement
for the three surfaces determined by these axes, and that G represents
the square of the ratio of enlargement of volume. Again, equation
(432) shows that E represents the sum of the squares of the ratios of
elongation for lines parallel to X', Y'} and Z' ; equation (434) shows
that F represents the sum of the squares of the ratios of enlargement
for surfaces parallel to the planes X'-Y', Y'-Z', Z'-X' '; and equation
(438), like (439), shows that G represents the square of the ratio of
G. i. o
210 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
enlargement of volume. Since the position of the co-ordinate axes
is arbitrary, it follows that the sum of the squares of the ratios of
elongation or enlargement of three lines or surfaces which in the
unstrained state are at right angles to one another, is otherwise
independent of the direction of the lines or surfaces. Hence, %E and
$F are the mean squares of the ratios of linear elongation and of
superficial enlargement, for all possible directions in the unstrained
solid.
There is not only a practical advantage in regarding the strain as
determined by E, F, and H, instead of E, F, and G, because H is
more simply expressed in terms of -,— ,, ... -*—,, but there is also a
certain theoretical advantage on the side of E, F, H. If the systems
of co-ordinate axes X, F, Z, and X', F', Z'y are either identical or
such as are capable of superposition, which it will always be con-
venient to suppose, the determinant H will always have a positive
value for any strain of which a body can be capable. But it is
possible to give to x, y, z such values as functions of x', y', z that H
shall have a negative value. For example, we may make
x=x', y = y', z=—z'. (440)
This will give H= — 1, while
x=x', y = y', z=*z' (441)
will give #=1. Both (440) and (441) give # = 1. Now although
such a change in the position of the particles of a body as is repre-
sented by (440) cannot take place while the body remains solid, yet
a method of representing strains may be considered incomplete,
which confuses the cases represented by (440) and (441).
We may avoid all such confusion by using E, F, and H to repre-
sent a strain. Let us consider an element of the body strained which
in the state (x', y', z') is a cube with its edges parallel to the axes of
X', Y', Z', and call the edges dx', dy', dz' according to the axes to
which they are parallel, and consider the ends of the edges as positive
for which the values of x', y', or z' are the greater. Whatever may
be the nature of the parallelepiped in the state (x, y, z) which corre-
sponds to the cube dx', dy', dz' and is determined by the quantities
-r->, ... -j-f, it may always be brought by continuous changes to the
d/x dz
form of a cube and to a position in which the edges dx', dy' shall
be parallel to the axes of X and Y, the positive ends of the edges
toward the positive directions of the axes, and this may be done
without giving the volume of the parallelepiped the value zero, and
therefore without changing the sign of H. Now two cases are
possible; — the positive end of the edge dz' may be turned toward
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 211
the positive or toward the negative direction of the axis of Z. In
the first case, H is evidently positive ; in the second, negative. The
determinant H will therefore be positive or negative, — we may say,
if we choose, that the volume will be positive or negative, — according
as the element can or cannot be brought from the state (x, y, z) to the
state (x'y yf, z') by continuous changes without giving its volume the
value zero.
If we now recur to the consideration of the principal axes of strain
and the principal ratios of elongation rt, r2, r8> and denote by Uly U2,
U3 and U^, U2, U3' the principal axes of strain in the strained and
unstrained element respectively, it is evident that the sign of rv
for example, depends upon the direction in Ul which we regard as
corresponding to a given direction in U^. If we choose to associate
directions in these axes so that rx, r2, rs shall all be positive, the
positive or negative value of H will determine whether the system of
axes Ulf U2, Us is or is not capable of superposition upon the system
£//, U2, U3' so that corresponding directions in the axes shall coincide.
Or, if we prefer to associate directions in the two systems of axes
so that they shall be capable of superposition, corresponding directions
coinciding, the positive or negative value of H will determine whether
an even or an odd number of the quantities rlt r2, r3 are negative.
In this case we may write
(442)
It will be observed that to change the signs of two of the quantities
ri» rz> rs ls simply to give a certain rotation to the body without
changing its state of strain.
Whichever supposition we make with respect to the axes Ult U2, U3,
it is evident that the state of strain is completely determined by the
values E, F, and H, not only when we limit ourselves to the consider-
ation of such strains as are consistent with the idea of solidity, but
also when we regard any values of -r— ,, ... -j-> as possible.
Approximative Formulce. — For many purposes the value of eV' for
an isotropic solid may be represented with sufficient accuracy by the
formula
6y, = i' + e'E +fF+ h'H, (443)
where i', e, /', and h' denote functions of qv> \ or ^ne value of i/rV' by
the formula
VTV, = i + eE+fF+ hH, (444)
dx
dx
dx
dx'
dy'
dz'
dy.
dx'
dy_
dy'
dy
dz'
dz
dz
dz
dxf
dz*
212 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
where i, e, /, and h denote functions of t. Let us first consider the
second of these formulae. Since E, F, and H are symmetrical functions
of rly rz, r8> if \fa> is any function of t, E, F, H, we must have
<&"!
^J2.f. ^72. /.
(445)
dr<?
drl dr2 ~ dfr2 drs ~~ dr% dr^
whenever r1 = r2 = r3. Now i, e, /, and h may be determined (as
functions of t) so as to give to
their proper values at every temperature for some isotropic state of
strain, which may be determined by any desired condition. We
shall suppose that they are determined so as to give the proper
values to i/rV'> etc-> when the stresses in the solid vanish. If we
denote by r0 the common value of rlt r2, rB which will make the
stresses vanish at any given temperature, and imagine the true value
of \l^>, and also the value given by equation (444) to be expressed in
terms of the ascending powers of
ri-ro> r2~n» r3-ro> (446)
it is evident that the expressions will coincide as far as the terms of
the second degree inclusive. That is, the errors of the values of >/>>
given by equation (444) are of the same order of magnitude as the
cubes of the above differences. The errors of the values of
dr1 ' dr2 ' drs
will be of the same order of magnitude as the squares of the same
differences. Therefore, since
d^, drl
^. B
-.dx " drl -jdx d/r% ..dx drs .,dx
dx' dx' dx' dx'
whether we regard the true value of \[sv, or the value given by equa-
tion (444), and since the error in (444) does not affect the values of
drl dr2 dr,
3
..dx' -.dx' -.dx'
dx' dx dx'
which we may regard as determined by equations (431), (432), (434),
(437) and (438), the errors in the values of X^, derived from (444)
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 213
will be of the same order of magnitude as the squares of the differ-
ences in (446). The same will be true with respect to XT, XZ', Y^,
etc., etc.
It will be interesting to see how the quantities e, /, and h are
related to those which most simply represent the elastic properties of
isotropic solids. If we denote by V and R the elasticity of volwme
and the rigidity* (both determined under the condition of constant
temperature and for states of vanishing stress), we shall have as
definitions
V= — v-- > when v = r03 v', (448)
where p denotes a uniform pressure to which the solid is subjected,
v its volume, and v' its volume in the state of reference ; and
' dx f-,dx\2'
a-j—, IM-J—/)
dy \ dy/
___ (449)
dx'~dy'~~dz'~''T^
rl/Y> rJ/Y> rJ/ti rl/ii rJ.v. fJ.v.
and
dx dy dz
when -r-/ = -^> = -r-, = r0,
dx dy dz
dx _dx _dy _dy _dz
dy' ~ dz' ~~ dz' ~ dx' ~ dx'
Now when the solid is subject to uniform pressure on all sides, if
we consider so much of it as has the volume unity in the state of
reference, we shall have
rt— rt—r§— «*, (450)
and by (444) and (439),
^v, = i + 3e<yf + 3/w* + hv. (451)
Hence, by equation (88), since i/rv, is equivalent to \fr,
(452)
. <463)
and by (448),
(454)
To obtain the value of R in accordance with the definition (449),
we may suppose the values of E, F, and H given by equations (432),
(434), and (437) to be substituted in equation (444). This will give
for the value of R
<
. (455)
See Thomson and Tail's Natural Philosophy, vol. i, p. 711.
214 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
Moreover, since p must vanish in (452) when /y = r03, we have
2e + 4/r02+&r0=0. (456)
From the three last equations may be obtained the values of e, f, ht
in terms of r0, Vy and R ; viz.,
h=-tR-V. (457)
The quantity r0, like J? and V, is a function of the temperature, the
differential coefficient — $ ° representing the rate of linear expansion
of the solid when without stress.
It will not be necessary to discuss equation (443) at length, as the
case is entirely analogous to that which has just been treated. (It
must be remembered that r]T, in the discussion of (443), will take the
place everywhere of the temperature in the discussion of (444).) If
we denote by V and R' the elasticity of volume and the rigidity,
both determined under the condition of constant entropy, (i.e., of no
transmission of heat,) and for states of vanishing stress, we shall
have the equations : —
*
, (458)
(459)
0
2e' + 4/V02 + feV0 = 0. (460)
Whence
S=*r,K-*r,r, /'=^^. h'=-%K-V. (461)
In these equations r0, R', and V are to be regarded as functions of
the quantity T/V>.
If we wish to change from one state of reference to another (also
isotropic), the changes required in the fundamental equation are easily
made. If a denotes the length of any line of the solid in the second
state of reference divided by its length in the first, it is evident that
when we change from the first state of reference to the second the
values of the symbols eV'> ^v> ^v> H are divided by a3, that of E
by a2, and that of F by a4. In making the change of the state of
reference, we must therefore substitute in the fundamental equation
of the form (444) a^T) a*E, a*F, o?H for ^T, E, F, and H,
respectively. In the fundamental equation of the form (443), we
must make the analogous substitutions, and also substitute aBr]T for
7/v'- (It will be remembered that i', e', f, and h' represent functions
of jjv>, and that it is only when their values in terms of 7/V' are
stituted, that equation (443) becomes a fundamental equation.)
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES, 215
Concerning Solids which absorb Fluids.
There are certain bodies which are solid with respect to some of
their components, while they have other components which are fluid.
In the following discussion, we shall suppose both the solidity and
the fluidity to be perfect, so far as any properties are concerned
which can affect the conditions of equilibrium, — i.e., we shall suppose
that the solid matter of the body is entirely free from plasticity
and that there are no passive resistances to the motion of the fluid
components except such as vanish with the velocity of the motion, —
leaving it to be determined by experiment how far and in what cases
these suppositions are realized.
It is evident that equation (356) must hold true with regard to
such a body, when the quantities of the fluid components contained
in a given element of the solid remain constant. Let IV, IV, etc.,
denote the quantities of the several fluid components contained in an
element of the body divided by the volume of the element in the
state of reference, or, in other words, let these symbols denote the
densities which the several fluid components would have, if the body
should be brought to the state of reference while the matter con-
tained in each element remained unchanged. We may then say that
equation (356) will hold true, when iy, IV, etc., are constant. The
complete value of the differential of eV' will therefore be given by an
equation of the form
de, =
a' + LbdTb' + etc. (462)
Now when the body is in a state of hydrostatic stress, the term in
this equation containing the signs of summation will reduce to
—pdvv. (VT denoting, as elsewhere, the volume of the element
divided by its volume in the state of reference). For in this case
xx,
,dx
J^y_dz__d?_^\
p\dy dz' dy'dz'J'
(463)
dz
pd
pd
dx
dx
dx
~dz'
dz~'
dz
dx'
dy'
dx'
dz
~S3
yv».
dy'
dz
dy'
dz'
(464)
216 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
We have, therefore, for a state of hydrostatic stress,
deT = t driT -p dvT+LadTa' + LbdTb' + etc., (465)
and multiplying by the volume of the element in the state of refer-
ence, which we may regard as constant,
de = tdrj--pdv-\-Ladma+Lbdmb+etc., (466)
where e, TJ, v, ma, mb, etc., denote the energy, entropy, and volume of
the element, and the quantities of its several fluid components. It is
evident that the equation will also hold true, if these symbols are
understood as relating to a homogeneous body of finite size. The
only limitation with respect to the variations is that the element or
body to which the symbols relate shall always contain the same solid
matter. The varied state may be one of hydrostatic stress or otherwise.
But when the body is in a state of hydrostatic stress, and the solid
matter is considered invariable, we have by equation (12)
= tdq —p dv -j- jmadma + /*&$?% + etc. (467)
It should be remembered that the equation cited occurs in a discussion
which relates only to bodies of hydrostatic stress, so that the varied
state as well as the initial is there regarded as one of hydrostatic
stress. But a comparison of the two last equations shows that the
last will hold true without any such limitation, and moreover, that
the quantities La, Lb, etc., when determined for a state of hydrostatic
stress, are equal to the potentials fj.a, fj.b, etc.
Since we have hitherto used the term potential solely with reference
to bodies of hydrostatic stress, we may apply this term as we choose
with regard to other bodies. We may therefore call the quantities
La, Lb, etc., the potentials for the several fluid components in the
body considered, whether the state of the body is one of hydrostatic
stress or not, since this use of the term involves only an extension of
its former definition. It will also be convenient to use our ordinary
symbol for a potential to represent these quantities. Equation (462)
may then be written
(468)
This equation holds true of solids having fluid components without
any limitation with respect to the initial state or to the variations,
except that the solid matter to which the symbols relate shall remain
the same.
In regard to the conditions of equilibrium for a body of this
kind, it is evident in the first place that if we make IV, Tb, etc.,
constant, we shall obtain from the general criterion of equilibrium
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 217
all the conditions which we have obtained for ordinary solids, and
which are expressed by the formulae (364), (374), (380), (382)-(384).
The quantities I\', F2', etc., in the last two formulae include of
course those which have just been represented by Ta', Fb', etc., and
which relate to the fluid components of the body, as well as the
corresponding quantities relating to its solid components. Again,
if we suppose the solid matter of the body to remain without
variation in quantity or position, it will easily appear that the
potentials for the substances which form the fluid components of the
solid body must satisfy the same conditions in the solid body and in
the fluids in contact with it, as in the case of entirely fluid masses.
See eqs. (22).
The above conditions must however be slightly modified in order to
make them sufficient for equilibrium. It is evident that if the solid
is dissolved at its surface, the fluid components which are set free may
be absorbed by the solid as well as by the fluid mass, and in like
manner if the quantity of the solid is increased, the fluid components
of the new portion may be taken from the previously existing solid
mass. Hence, whenever the solid components of the solid body are
actual components of the fluid mass, (whether the case is the same
with the fluid components of the solid body or not,) an equation of
the form (383) must be satisfied, in which the potentials [jLa, fjLb, etc.,
contained implicitly in the second member of the equation are deter-
mined from the solid body. Also if the solid components of the
solid body are all possible but not all actual components of the fluid
mass, a condition of the form (384) must be satisfied, the values of the
potentials in the second member being determined as in the preceding
case.
The quantities
t, XK,, ...Zz, fjia) yu6, etc., (469)
being differential coefficients of eV' with respect to the variables
(470)
will of course satisfy the necessary relations
dt
, etc. (471)
.
dx
This result may be generalized as follows. Not only is the second
member of equation (468) a complete differential in its present form,
but it will remain such if we transfer the sign of differentiation (d)
from one factor to the other of any term (the sum indicated by the
218 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
symbol 22' is here supposed to be expanded into nine terms), and
at the same time change the sign of the term from + to — . For to
substitute —jjydt for tdqT, for example, is equivalent to subtracting
the complete differential d(trjT). Therefore, if we consider the quan-
tities in (469) and (470) which occur in any same term in equation
(468) as forming a pair, we may choose as independent variables
either quantity of each pair, and the differential coefficient of the
remaining quantity of any pair with respect to the independent
variable of another pair will be equal to the differential coefficient
of the remaining quantity of the second pair with respect to the
independent variable of the first, taken positively, if the independent
variables of these pairs are both affected by the sign d in equation
(468), or are neither thus affected, but otherwise taken negatively.
Thus
idTa
(473)
where in addition to the quantities indicated by the suffixes, the
following are to be considered as constant: — either t or qv,, either
XT or -T-,, ... either Zz> or -^-7, either jnb or IY, etc.
It will be observed that when the temperature is constant the
conditions jULa = const., yu& = const., represent the physical condition of
a body in contact with a fluid of which the phase does not vary, and
which contains the components to which the potentials relate. Also
that when IY, IY, etc., are constant, the heat absorbed by the body
in any infinitesimal change of condition per unit of volume measured
in the state of reference is represented by tdqv,. If we denote this
quantity by dQT, and use the suffix Q to denote the condition of no
transmission of heat, we may write
ax' /y
where IY, IY, etc., must be regarded as constant in all the equations,
and either XT or -7-7, . . . either Zz> or -^—n in each equation.
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 219
Influence of Surfaces of Discontinuity upon the Equilibrium of
Heterogeneous Masses. — Theory of Capillarity.
We have hitherto supposed, in treating of heterogeneous masses in
contact, that they might be considered as separated by mathematical
surfaces, each mass being unaffected by the vicinity of the others,
so that it might be homogeneous quite up to the separating surfaces
both with respect to the density of each of its various components
and also with respect to the densities of energy and entropy. That
such is not rigorously the case is evident from the consideration that
if it were so with respect to the densities of the components it could
not be so in general with respect to the density of energy, as the
sphere of molecular action is not infinitely small. But we know from
observation that it is only within very small distances of such a
surface that any mass is sensibly affected by its vicinity, — a natural
consequence of the exceedingly small sphere of sensible molecular
action, — and this fact renders possible a simple method of taking
account of the variations in the densities of the component substances
and of energy and entropy, which occur in the vicinity of surfaces
of discontinuity. We may use this term, for the sake of brevity,
without implying that the discontinuity is absolute, or that the term
distinguishes any surface with mathematical precision. It may be
taken to denote the non-homogeneous film which separates homo-
geneous or nearly homogeneous masses.
Let us consider such a surface of discontinuity in a fluid mass
which is in equilibrium and uninfluenced by gravity. For the precise
measurement of the quantities with which we have to do, it will be
convenient to be able to refer to a geometrical surface, which shall be
sensibly coincident with the physical surface of discontinuity, but
shall have a precisely determined position. For this end, let us take
some point in or very near to the physical surface of discontinuity,
and imagine a geometrical surface to pass through this point and
all other points which are similarly situated with respect to the
condition of the adjacent matter. Let this geometrical surface be
called the dividing surface, and designated by the symbol S. It
will be observed that the position of this surface is as yet to a certain
extent arbitrary, but that the directions of its normals are already
everywhere determined, since all the surfaces which can be formed in
the manner described are evidently parallel to one another. Let us
also imagine a closed surface cutting the surface S and including a
part of the homogeneous mass on each side. We will so far limit the
form of this closed surface as to suppose that on each side of S, as far
as there is any want of perfect homogeneity in the fluid masses, the
closed surface is such as may be generated by a moving normal to S.
220 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
Let the portion of S which is included by the closed surface be
denoted by S, and the area of this portion by a. Moreover, let the
mass contained within the closed surface be divided into three parts
by two surfaces, one on each side of S, and very near to that surface,
although at such distance as to lie entirely beyond the influence of
the discontinuity in its vicinity. Let us call the part which contains
the surface S (with the physical surface of discontinuity) M, and the
homogeneous parts M' and M", and distinguish by e, e', e", q, rf, q",
mv ra/, ra/', m2, m2', m2", etc., the energies and entropies of these
masses, and the quantities which they contain of their various
components.
It is necessary, however, to define more precisely what is to be
understood in cases like the present by the energy of masses which
are only separated from other masses by imaginary surfaces. A part
of the total energy which belongs to the matter in the vicinity of the
separating surface, relates to pairs of particles which are on different
sides of the surface, and such energy is not in the nature of things
referable to either mass by itself. Yet, to avoid the necessity of
taking separate account of such energy, it will often be convenient to
include it in the energies which we refer to the separate masses.
When there is no break in the homogeneity at the surface, it is
natural to treat the energy as distributed with a uniform density.
This is essentially the case with the initial state of the system which
we are considering, for it has been divided by surfaces passing in
general through homogeneous masses. The only exception — that of
the surface which cuts at right angles the non-homogeneoiis film —
(apart from the consideration that without any important loss of
generality we may regard the part of this surface within the film as
very small compared with the other surfaces) is rather apparent than
real, as there is no change in the state of the matter in the direction
perpendicular to this surface. But in the variations to be considered
in the state of the system, it will not be convenient to limit ourselves
to such as do not create any discontinuity at the surfaces bounding
the masses M, M', M"; we must therefore determine how we will
estimate the energies of the masses in case of such infinitesimal
discontinuities as may be supposed to arise. Now the energy of
each mass will be most easily estimated by neglecting the discon-
tinuity, i.e., if we .estimate the energy on the supposition that
beyond the bounding surface the phase is identical with that within
the surface. This will evidently be allowable, if it does not affect
the total amount of energy. To show that it does not affect this
quantity, we have only to observe that, if the energy of the mass on
one side of a surface where there is an infinitesimal discontinuity of
phase is greater as determined by this rule than if determined by
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 221
any other (suitable) rule, the energy of the mass on the other side
must be less by the same amount when determined by the first rule
than when determined by the second, since the discontinuity relative
to the second mass is equal but opposite in character to the discon-
tinuity relative to the first.
If the entropy of the mass which occupies any one of the spaces
considered is not in the nature of things determined without refer-
ence to the surrounding masses, we may suppose a similar method
to be applied to the estimation of entropy.
With this understanding, let us return to the consideration of the
equilibrium of the three masses M, M', and M". We shall suppose
that there are no limitations to the possible variations of the system
due to any want of perfect mobility of the components by means of
which we express the composition of the masses, and that these com-
ponents are independent, i.e., that no one of them can be formed out
of the others. ^
With regard to the mass M, which includes the surface of discon-
tinuity, it is necessary for its internal equilibrium that when its
boundaries are considered constant, and when we consider only
reversible variations (i.e., those of which the opposite are also
possible), the variation of its energy should vanish with the variations
of its entropy and of the quantities of its various components.
For changes within this mass will not affect the energy or the entropy
of the surrounding masses (when these quantities are estimated on
the principle which we have adopted), and it may therefore be
treated as an isolated system. For fixed boundaries of the mass M,
and for reversible variations, we may therefore write
Se^A^ri+A^m^+A^mz+Qtc., (476)
where AQ, Alt A2, etc., are quantities determined by the initial
(unvaried) condition of the system. It is evident that A0 is the
temperature of the lamelliform mass to which the equation relates,
or the temperature at the surface of discontinuity. By comparison
of this equation with (12) it will be seen that the definition of A19
A2, etc., is entirely analogous to that of the potentials in homo-
geneous masses, although the mass to which the former quantities
relate is not homogeneous, while in our previous definition of
potentials, only homogeneous masses were considered. By a natural
extension of the term potential, we may call the quantities Al,A2, etc.,
the potentials at the surface of discontinuity. This designation will
be farther justified by the fact, which will appear hereafter, that the
value of these quantities is independent of the thickness of the lamina
(M) to which they relate. If we employ our ordinary symbols for
temperature and potentials, we may write
(477)
222 EQUILIBKIUM OF HETEROGENEOUS SUBSTANCES.
If we substitute 2: for = in this equation, the formula will hold
true of all variations whether reversible or not ;* for if the variation
of energy could have a value less than that of the second member of
the equation, there must be variation in the condition of M in which
its energy is diminished without change of its entropy or of the
quantities of its various components.
It is important, however, to observe that for any given values of
Sri, Smly Sm2, etc., while there may be possible variations of the
nature and state of M for which the value of Se is greater than that
of the second member of (477), there must always be possible varia-
tions for which the value of Se is equal to that of the second member.
It will be convenient to have a notation which will enable us to
express this by an equation. Let be denote the smallest value (i.e., the
value nearest to — oo ) of Se consistent with given values of the other
variations, then
be = tSr)-^-iuLl Sm1 + fi28mz+ etc. (478)
For the internal equilibrium of the whole mass which consists of
the parts M, M', M", it is necessary that
&+&' + &"^0 (479)
for all variations which do not affect the enclosing surface or the
total entropy or the total quantity of any of the various components.
If we also regard the surfaces separating M, M', and M" as invariable,
we may derive from this condition, by equations (478) and (12), the
following as a necessary condition of equilibrium : —
j + fjL2 $m2 + etc.
. ^ 0, (480)
* To illustrate the difference between variations which are reversible, and those which
are not, we may conceive of two entirely different substances meeting in equilibrium
at a mathematical surface without being at all mixed. We may also conceive of
them as mixed in a thin film about the surface where they meet, and then the amount
of mixture is capable of variation both by increase and by diminution. But when they
are absolutely unmixed, the amount of mixture can be increased, but is incapable of
diminution, and it is then consistent with equilibrium that the value of 5e (for a
variation of the system in which the substances commence to mix) should be greater than
the second member of (477). It is not necessary to determine whether precisely such
cases actually occur ; but it would not be legitimate to overlook the possible occurrence
of cases in which variations may be possible while the opposite variations are not.
It will be observed that the sense in which the term reversible is here used is entirely
different from that in which it is frequently used in treatises on thermodynamics,
where a process by which a system is brought from a state A to a state B is called
reversible, to signify that the system may also be brought from the state B to the state
A through the same series of intermediate states taken in the reverse order by means of
external agencies of the opposite character. The variation of a system from a state A
to a state B (supposed to differ infinitely little from the first) is here called reversible
when the system is capable of another state B' which bears the same relation to the
state A that A bears to B.
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 223
the variations being subject to the equations of condition
(481)
-\-6/m2 —V>
etc.
It may also be the case that some of the quantities Sm^, Sm^',
#m2", etc., are incapable of negative values or can only have the
value zero. This will be the case when the substances to which these
quantities relate are not actual or possible components of M' or M".
(See page 64.) To satisfy the above condition it is necessary and
sufficient that
t = t' = t", (482)
2' , etc., (483)
//2''(Sm2''^jM2<$m2'', etc. (484)
It will be observed that, if the substance to which JULV for instance,
relates is an actual component of each of the homogeneous masses,
we shall have A4 = /*/ = /*i"- If it is an actual component of the
first only of these masses, we shall have /^1 = /w1/. If it is also a
possible component of the second homogeneous mass, we shall also
have /*! = ///'. If this substance occurs only at the surface of dis-
continuity, the value of the potential //x will not be determined by
any equation, but cannot be greater than the potential for the same
substance in either of the homogeneous masses in which it may be a
possible component.
It appears, therefore, that the particular conditions of equilibrium
relating to temperature and the potentials which we have before
obtained by neglecting the influence of the surfaces of discontinuity
(pp. 65, 66, 74) are not invalidated by the influence of such dis-
continuity in their application to homogeneous parts of the system
bounded like M' and M" by imaginary surfaces lying within the limits
of homogeneity, — a condition which may be fulfilled by surfaces very
near to the surfaces of discontinuity. It appears also that similar
conditions will apply to the non-homogeneous films like M, which
separate such homogeneous masses. The properties of such films,
which are of course different from those of homogeneous masses,
require our farther attention.
The volume occupied by the mass M is divided by the surface 3
into two parts which we will call v'" and v"", v'" lying next to M',
and v"" to M". Let us imagine these volumes filled by masses having
throughout the same temperature, pressure and potentials, and the
same densities of energy and entropy, and of the various components,
224 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
as the masses M' and M" respectively. We shall then have, by
equation (12), if we regard the volumes as constant,
M" = t'W + fr'tonS" + ju2'<$m2'" + etc., (485)
&"" = tf'W" + fr" tonS'" + //2"<5m2"" + etc. ; (486)
whence, by (482)-(484), we have for reversible variations
(487)
(488)
From these equations and (477), we have for reversible variations
S(e - e'" - e"") = tS(rj- if" - i'")
+ /^(^i - m/" - m/'") + fJL2 8(m2 - m2'" - m2"") + etc. (489)
Or, if we set*
fiB^c-e'"-^'", n* = ri-ri"f-ri"", (490)
mf = mx — m/" — m/'", mf = m2 — m2'" — m2"", etc., (491 )
we may write
Se8 = t8tjs + frSm* + fr&mS + etc. (492)
This is true of reversible variations in which the surfaces which have
been considered are fixed. It will be observed that es denotes the
excess of the energy of the actual mass which occupies the total
volume which we have considered over that energy which it would
have, if on each side of the surface S the density of energy had the
same uniform value quite up to that surface which it has at a sensible
distance from it ; and that qs, mf, mf> etc., have analogous significations.
It will be convenient, and need not be a source of any misconception,
to call es and T/S the energy and entropy of the surface (or the super-
pO w&
ficial energy and entropy), — and — the superficial densities of energy
s s
77v 77i
and entropy, -— , -— , etc., the superficial densities of the several com-
ponents.
Now these quantities (es, if, mf, etc.) are determined partly by the
state of the physical system which we are considering, and partly by
the various imaginary surfaces by means of which these quantities
have been defined. The position of these surfaces, it will be remem-
bered, has been regarded as fixed in the variation of the system. It
is evident, however, that the form of that portion of these surfaces
which lies in the region of homogeneity on either side of the surface
of discontinuity cannot affect the values of these quantities. To
obtain the complete value of <Se8 for reversible variations, we have
*It will be understood that the 8 here used is not an algebraic exponent, but is
only intended as a distinguishing mark. The Roman letter S has not been used to
denote any quantity.
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 225
therefore only to regard variations in the position and form of the
limited surface s, as this determines all of the surfaces in question
lying within the region of non-homogeneity. Let us first suppose
the form of s to remain unvaried and only its position in space to
vary, either by translation or rotation. No change in (492) will be
necessary to make it valid in this case. For the equation is valid if
8 remains fixed and the material system is varied in position ; also, if
the material system and s are both varied in position, while their
relative position remains unchanged. Therefore, it will be valid if
the surface alone varies its position.
But if the form of s be varied, we must add to the second member
of (492) terms which shall represent the value of
SeB — tSrj8 — /Zj Smf — /z2#mf — etc.
due to such variation in the form of S. If we suppose S to be suffi-
ciently small to be considered uniform throughout in its curvatures-
and in respect to the state of the surrounding matter, the value of
the above expression will be determined by the variation of its area
$s and the variations of its principal curvatures 8c^ and 8c2, and
we may write
£raf -f etc.
c, + <72 Sc2 , (493)
or
Ses = tSriB + fjL1 (5m? + /UL2 #mf + etc.
+<r38+l(Cl + Ct)3(cl + Ci)+l(Cl-Cs)t(cl-ct), (494)
or, C\, and (72 denoting quantities which are determined by the initial
state of the system and the position and form of s. The above is
the complete value of the variation of e8 for reversible variations
of the system. But it is always possible to give such a position to
the surface s that Cl-\-C2 shall vanish.
To show this, it will be convenient to write the equation in the
longer form {see (490), (491)}
de—iSy — fa 8^ — /jL2 3m2 — etc.
8rf" + fr Sm^" + H2Sm2'" + etc.
i.e., by (482X484) and (12),
- etc.
(496)
From this equation it appears in the first place that the pressure
is the same in the two homogeneous masses separated by a plane
G. i. p
226 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
surface of discontinuity. For let us imagine the material system to
remain unchanged, while the plane surface s without change of area
or of form moves in the direction of its normal. As this does not
affect the boundaries of the mass M,
Also Ss = 0, <$0i + c2) = 0, 5(cx - c2) = 0, and 8v"f = - &/"'. Hence p' =p",
when the surface of discontinuity is plane.
Let us now examine the effect of different positions of the surface 3
in the same material system upon the value of C^ + C^, supposing at
first that in the initial state of the system the surface of discontinuity
is plane. Let us give the surface S some particular position. In the
initial state of the system this surface will of course be plane like
the physical surface of discontinuity, to which it is parallel. In the
varied state of the system, let it become a portion of a spherical
surface having positive curvature ; and at sensible distances from this
surface let the matter be homogeneous and with the same phases as
in the initial state of the system ; also at and about the surface let
the state of the matter so far as possible be the same as at and about
the plane surface in the initial state of the system. (Such a variation
in the system may evidently take place negatively as well as posi-
tively, as the surface may be curved toward either side. But whether
such a variation is consistent with the maintenance of equilibrium
is of no consequence, since in the preceding equations only the initial
state is supposed to be one of equilibrium.) Let the surface S, placed
as supposed, whether in the initial or the varied state of the surface,
be distinguished by the symbol s'. Without changing either the
initial or the varied state of the material system, let us make another
supposition with respect to the imaginary surface S. In the unvaried
system let it be parallel to its former position but removed from it
a distance X on the side on which lie the centers of positive curvature.
In the varied state of the system, let it be spherical and concentric
with s', and separated from it by the same distance X. It will of
course lie on the same side of s' as in the unvaried system. Let the
surface S, placed in accordance with this second supposition, be
distinguished by the symbol c". Both in the initial and the varied
state, let the perimeters of s' and s" be traced by a common normal.
Now the value of
Se — tSq — fji! S^ — fjL2 $m2 — etc.
in equation (496) is not affected by the position of S, being deter-
mined simply by the body M. The same is true of p' &vf" +p" 8v"" or
p'S(v'"+v"")} v'"+<u"" being the volume of M. Therefore the second
member of (496) will have the same value whether the expressions
relate to s' or s". Moreover, ^(c1 — c2) = 0 both for s' and s". If
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 227
we distinguish the quantities determined for s' and for B" by the
marks ' and ", we may therefore write
<r'#+i(0/+<V)*(V+^><^^
Now if we make 8s" = 0,
we shall have by geometrical necessity
Hence
</*x ^"+0+ ^1'+ tf20 ^
But 8(Ci + c2') = S(ci + c2") .
Therefore, <Y + <72' + 2o-'sX = <?/' + C2".
This equation shows that we may give a positive or negative value
to C^'H-Cg" by placing s" a sufficient distance on one or on the other
side of s'. Since this is true when the (unvaried) surface is plane,
it must also be true when the surface is nearly plane. And for this
purpose a surface may be regarded as nearly plane, when the radii
of curvature are very large in proportion to the thickness of the
non-homogeneous film. This is the case when the radii of curvature
have any sensible size. In general, therefore, whether the surface of
discontinuity is plane or curved it is possible to place the surface 8
so that C^-hCg in equation (494) shall vanish.
Now we may easily convince ourselves by equation (493) that if S
is placed within the non-homogeneous film, and s = l, the quantity or
is of the same order of magnitude as the values of e8, if, m8, mf, etc.,
while the values of Cl and C2 are of the same order of magnitude
as the changes in the values of the former quantities caused by
increasing the curvature of S by unity. Hence, on account of the
thinness of the non-homogeneous film, since it can be very little
affected by such a change of curvature in s, the values of Gl and C2
must in general be very small relatively to cr. And hence, if s' be
placed within the non-homogeneous film, the value of \ which will
make C/' + C^" vanish must be very small (of the same order of
magnitude as the thickness of the non-homogeneous film). The
position of s, therefore, which will make Oj + Cg in (494) vanish,
will in general be sensibly coincident with the physical surface of
discontinuity.
We shall hereafter suppose, when the contrary is not distinctly
indicated, that the surface S, in the unvaried state of the system, has
such a position as to make (71 + 02 = 0. It will be remembered that
the surface s is a part of a larger surface S, which we have called the
dividing surface, and which is coextensive with the physical surface
of discontinuity. We may suppose that the position of the dividing
surface is everywhere determined by similar considerations. This
228 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
is evidently consistent with the suppositions made on page 219 with
regard to this surface.
We may therefore cancel the term
in (494). In regard to the following term, it will be observed that
Cl must necessarily be equal to G2, when c^ — c^, which is the case
when the surface of discontinuity is plane. Now on account of the
thinness of the non-homogeneous film, we may always regard it as
composed of parts which are approximately plane. Therefore, without
danger of sensible error, we may also cancel the term
Equation (494) is thus reduced to the form
Ses = tSn8 + o-Ss + fjL1S'm% + iuL2S>m% + etc. (497)
We may regard this as the complete value of Ses, for all reversible
variations in the state of the system supposed initially in equilibrium,
when the dividing surface has its initial position determined in the
manner described.
The above equation is of fundamental importance in the theory
of capillarity. It expresses a relation with regard to surfaces of
discontinuity analogous to that expressed by equation (12) with
regard to homogeneous masses. From the two equations may be
directly deduced the conditions of equilibrium of heterogeneous
masses in contact, subject or not to the action of gravity, without
disregard of the influence of the surfaces of discontinuity. The
general problem, including the action of gravity, we shall take up
hereafter ; at present we shall only consider, as hitherto, a small part
of a surface of discontinuity with a part of the homogeneous mass
on either side, in order to deduce the additional condition which
may be found when we take account of the motion of the dividing
surface.
We suppose as before that the mass especially considered is
bounded by a surface of which all that lies in the region of non-
homogeneity is such as may be traced by a moving normal to the
dividing surface. But instead of dividing the mass as before into
four parts, it will be sufficient to regard it as divided into two
parts by the dividing surface. The energy, entropy, etc., of these
parts, estimated on the supposition that its nature (including
density of energy, etc.) is uniform quite up to the dividing surface,
will be denoted by e', jy', etc., e", r\ ', etc. Then the total energy will
be e8 + e' -f e", and the general condition of internal equilibrium will be
that
^0, (498)
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 229
when the bounding surface is fixed, and the total entropy and total
quantities of the various components are constant. We may suppose
Vs, n'> n"> m?> mi'» mi"> mf> m2'> m2"> e^c-' t° k6 ftU constant. Then
by (497) and (12) the condition reduces to
a- 8s -p'Sv' -p"Sv" = 0. (499)
(We may set = for ^, since changes in the position of the dividing
surface can evidently take place in either of two opposite directions.)
This equation has evidently the same form as if a membrane without
rigidity and having a tension or, uniform in all directions, existed
at the dividing surface. Hence the particular position which we
have chosen for this surface may be called the surface of tension, and
<r the superficial tension. If all parts of the dividing surface move a
uniform normal distance SN, we shall have
to = (<?! + c2)s SN, Sv' = s SN, Sv" =-sSN;
whence <r(cl+cz)=p' — p", (500)
the curvatures being positive when their centers lie on the side to
which p' relates. This is the condition which takes the place of that
of equality of pressure (see pp. 65, 74) for heterogeneous fluid
masses in contact, when we take account of the influence of the
surfaces of discontinuity. We have already seen that the conditions
relating to temperature and the potentials are not affected by these
surfaces.
Fundamental Equations for Surfaces of Discontinuity between
Fluid Masses.
In equation (497) the initial state of the system is supposed to be
one of equilibrium. The only limitation with respect to the varied
state is that the variation shall be reversible, i.e., that an opposite
variation shall be possible. Let us now confine our attention to
variations in which the system remains in equilibrium. To dis-
tinguish this case, we may use the character d instead of S, and write
de8 = t drjB + a-ds+[jLl dmf + JULZ dm% -f etc. (501 )
Both the states considered being states of equilibrium, the limitation
with respect to the reversibility of the variations may be neglected,
since the variations will always be reversible in at least one of the
states considered.
If we integrate this equation, supposing the area s to increase from
zero to any finite value s, while the material system to a part of
which the equation relates remains without change, we obtain
(502)
230 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
which may be applied to any portion of any surface of discontinuity
(in equilibrium) which is of the same nature throughout, or through-
out which the values of t, a; fJ.l) /m2, etc., are constant.
If we differentiate this equation, regarding all the quantities as
variable, and compare the result with (501), we obtain
rf1 dt + sdv-\- m?cfy/1-fmfcZya2 + etc. = 0. (503)
If we denote the superficial densities of energy, of entropy, and of
the several component substances (see page 224) by es, ijS) Tlt T2, etc.,
we have
€g = ^, %=3-, (504)
]?! = —, r2 =— , etc., (505)
and the preceding equations may be reduced to the form
(506)
+ etc., (507)
da- = — J]8dt — ric?yw1 — T%djUL2 — etc. (508)
Now the contact of the two homogeneous masses does not impose
any restriction upon the variations of phase of either, except that
the temperature and the potentials for actual components shall have
the same value in both. {See (482)-(484) and (500).} For however
the values of the pressures in the homogeneous masses may vary (on
account of arbitrary variations of the temperature and potentials),
and however the superficial tension may vary, equation (500) may
always be satisfied by giving the proper curvature to the surface of
tension, so long, at least, as the difference of pressures is not great.
Moreover, if any of the potentials JULI, ju.2) etc., relate to substances
which are found only at the surface of discontinuity, their values
may be varied by varying the superficial densities of those sub-
stances. The values of t, JULI} JULZ) etc., are therefore independently
variable, and it appears from equation (508) that o- is a function of
these quantities. If the form of this function is known, we may
derive from it by differentiation n+I equations (n denoting the total
number of component substances) giving the values of ?/s, I\, F2,
etc., in terms of the variables just mentioned. This will give us,
with (507), 7i+3 independent equations between the 2^ + 4 quantities
which occur in that equation. These are all that exist, since n + l
of these quantities are independently variable. Or, we may consider
that we have n+3 independent equations between the 2n+5 quan-
tities occurring in equation (502), of which n + 2 are independently
variable.
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 231
An equation, therefore, between
o-, t, yUj, //2, etc., (509)
may be called a fundamental equation for the surface of discontinuity.
An equation between
e8, if, s, raf, mf, etc., (510)
or between es, jys, I\, F2, etc. (511)
may also be called a fundamental equation in the same sense. For
it is evident from (501) that an equation may be regarded as sub-
sisting between the variables (510), and if this equation be known,
since 7i-t-2 of the variables may be regarded as independent (viz.,
n+1 for the n+1 variations in the nature of the surface of dis-
continuity, and one for the area of the surface considered), we may
obtain by differentiation and comparison with (501), n + 2 additional
equations between the 2n + 5 quantities occurring in (502). Equation
(506) shows that equivalent relations can be deduced from an equation
between the variables (511). It is moreover quite evident that an
equation between the variables (510) must be reducible to the form
of an equation between the ratios of these variables, and therefore to
an equation between the variables (511).
The same designation may be applied to any equation from which,
by differentiation and the aid only of general principles and relations,
7i+3 independent relations between the same 2n+5 quantities may
be obtained.
If we set V8 = *S-^S> (512)
we obtain by differentiation and comparison with (501)
d\fs8 = — j?8 dt + o- ds + fadm^ + /UL2dm% + etc. (513)
An equation, therefore, between \[sa, t, s, mf, mf, etc., is a fundamental
equation, and is to be regarded as entirely equivalent to either of the
other fundamental equations which have been mentioned.
The reader will not fail to notice the analogy between these funda-
mental equations, which relate to surfaces of discontinuity, and those
relating to homogeneous masses, which have been described on pages
85-89.
On the Experimental Determination of Fundamental Equations for
Surfaces of Discontinuity between Fluid Masses.
When all the substances which are found at a surface of discon-
tinuity are components of one or the other of the homogeneous
masses, the potentials /x1, yM2, etc., as well as the temperature, may
be determined from these homogeneous masses.* The tension a- may
* It is here supposed that the thermodynamic properties of the homogeneous masses
have already been investigated, and that the fundamental equations of these masses
may be regarded as known.
232 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
be determined by means of the relation (500). But our measure-
ments are practically confined to cases in which the difference of the
pressures in the homogeneous masses is small; for with increasing
differences of pressure the radii of curvature soon become too small
for measurement. Therefore, although the equation p' =p" (which
is equivalent to an equation between t, fjLv /z2, etc., since p' and p"
are both functions of these variables) may not be exactly satisfied
in cases in which it is convenient to measure the tension, yet this
equation is so nearly satisfied in all the measurements of tension
which we can make, that we must regard such measurements as
simply establishing the values of a- for values of t, fa, /*2, etc., which
satisfy the equation p' =p' ', but not as sufficient to establish the rate
of change in the value of a- for variations of t, JULI} JULZ, etc., which are
inconsistent with the equation p' =p".
To show this more distinctly, let t, JULZ, m3, etc., remain constant,
then by (508) and (98)
m ra
y/ and y/' denoting the densities — f and — \r> Hence,
and I\d(y -p") = (y/' - y/) AT.
But by (500)
(ci + cz) dor + or d(c: + c2) = d(p' —p").
Therefore,
Afci + c2) da- + IV d(Ci + c2) = (y/' - Vl') dor,
or (y" - y/ - F^C! + C2)} dor = I> d(c1 + C2).
Now ^(Cj+Cg) will generally be very small compared with y/' —
Neglecting the former term, we have
dcr _ I\ 7, v
— — 77 7^\ci~rCz).
<r Vi -Vi
To integrate this equation, we may regard Tlt y/, y/ as constant
This will give, as an approximate value,
1
Vi "Vi
o-' denoting the value of o- when the surface is plane. From this it
appears that when the radii of curvature have any sensible magni-
tude, the value of u will be sensibly the same as when the surface is
plane and the temperature and all the potentials except one have
the same values, unless the component for which the potential has
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 233
not the saine value has very nearly the same density in the two
homogeneous masses, in which case, the condition under which the
variations take place is nearly equivalent to the condition that the
pressures shall remain equal.
Accordingly, we cannot in general expect to determine the
/d<r\ *
superficial density I\ from its value — ( -j — ) by measurements of
**thf*, /*
superficial tensions. The case will be the same with F2, rs, etc., and
also with TJS, the superficial density of entropy.
The quantities es, */s, I\, F2, etc., are evidently too small in general
to admit of direct measurement. When one of the components,
however, is found only at the surface of discontinuity, it may be
more easy to measure its superficial density than its potential. But
except in this case, which is of secondary interest, it will generally
be easy to determine <r in terms of t, fa, fa, etc., with considerable
accuracy for plane surfaces, and extremely difficult or impossible to
determine the fundamental equation more completely.
Fundamental Equations for Plane Surfaces of Discontinuity
between Fluid Masses.
An equation giving <r in terms of t, fa, fa, etc., which will hold
true only so long as the surface of discontinuity is plane, may be
called a fundamental equation for a plane surface of discontinuity.
It will be interesting to see precisely what results can be obtained
from such an equation, especially with respect to the energy and
entropy and the quantities of the component substances in the
vicinity of the surface of discontinuity.
These results can be exhibited in a more simple form, if we deviate
to a certain extent from the method which we have been following.
The particular position adopted for the dividing surface (which
determines the superficial densities) was chosen in order to make the
term ^(Gl-{-C2)8(c1-\-c2) in (494) vanish. But when the curvature
of the surface is not supposed to vary, such a position of the dividing
surface is not necessary for the simplification of the formula. It is
evident that equation (501) will hold true for plane surfaces (supposed
to remain such) without reference to the position of the dividing
surface, except that it shall be parallel to the surface of discontinuity.
We are therefore at liberty to choose such a position for the dividing
surface as may for any purpose be convenient.
None of the equations (502)-(513), which are either derived from
(501), or serve to define new symbols, will be affected by such a
* The suffixed fj. is used to denote that all the potentials except that occurring in the
denominator of the differential coefficient are to be regarded as constant.
234 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
change in the position of the dividing surface. But the expressions
e8, i/s, mf, mf, etc., as also es, ij8, Tlt F2, etc., and \/rs, will of course
have different values when the position of that surface is changed.
The quantity cr, however, which we may regard as defined by equa-
tions (501), or, if we choose, by (502) or (507), will not be affected in
value by such a change. For if the dividing surface be moved a
distance X measured normally and toward the side to which v" relates,
the quantities
eg, j/s, T19 F2, etc.,
will evidently receive the respective increments
X(ev"-ev'), x(W-*v), My/'-y/X My2"-y2')> etc.,
£y'> ev"> tfv'> n\" denoting the densities of energy and entropy in the
two homogeneous masses. Hence, by equation (507), <r will receive
the increment
But by (93)
-p" = ev" - trjy" - fj.l7l" - fryf - etc.,
-pf = ev' - triv - //iy/ - //2y2' - etc.
Therefore, since p'=p", the increment in the value of a- is zero.
The value of cr is therefore independent of the position of the dividing
surface, when this surface is plane. But when we call this quantity
the superficial tension, we must remember that it will not have
its characteristic properties as a tension with reference to any arbitrary
surface. Considered as a tension, its position is in the surface which
we have called the surface of tension, and, strictly speaking, nowhere
else. The positions of the dividing surface, however, which we shall
consider, will not vary from the surface of tension sufficiently to
make this distinction of any practical importance.
It is generally possible to place the dividing surface so that the
total quantity of any desired component in the vicinity of the surface
of discontinuity shall be the same as if the density of that component
were uniform on each side quite up to the dividing surface. In other
words, we may place the dividing surface so as to make any one of
the quantities Tlt F2, etc., vanish. The only exception is with regard
to a component which has the same density in the two homogeneous
masses. With regard to a component which has very nearly the
same density in the two masses such a location of the dividing surface
might be objectionable, as the dividing surface might fail to coincide
sensibly with the physical surface of discontinuity. Let us suppose
that y/ is not equal (nor very nearly equal) to y/', and that the
dividing surface is so placed as to make F: = 0. Then equation (508)
reduces to
(514)
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 235
where the symbols j/8(1), F2(1), etc., are used for greater distinctness to
denote the values of qa, F2, etc., as determined by a dividing surface
placed so that F^O. Now we may consider all the differentials in
the second member of this equation as independent, without violating
the condition that the surface shall remain plane, i.e., that dp' = dp".
This appears at once from the values of dp' and dp" given by equation
(98). Moreover, as has already been observed, when the fundamental
equations of the two homogeneous masses are known, the equation
p'=p" affords a relation between the quantities t, fa, fJL2, etc. Hence,
when the value of o- is also known for plane surfaces in terms of
t, fa, yu2, etc., we can eliminate fa from this expression by means of
the relation derived from the equality of pressures, and obtain the
value of a for plane surfaces in terms of t, /*2, /i3, etc. From this,
by differentiation, we may obtain directly the values of rj&(l), r2(D, T3(l),
etc., in terms of t, //2, /*3, etc. This would be a convenient form of
the fundamental equation. But, if the elimination of p', p", and fa
from the finite equations presents algebraic difficulties, we can in all
cases easily eliminate dp', dp", dfa from the corresponding differential
equations and thus obtain a differential equation from which the
values of ^S(1), F2(i), F3(1), etc., in terms of t, fa, //2, etc., may be at once
obtained by comparison with (514).*
* If liquid mercury meets the mixed vapors of water and mercury in a plane surface,
and we use /^ and ^ to denote the potentials of mercury and water respectively, and
place the dividing surface so that I\ = 0, i.e., so that the total quantity of mercury is
the same as if the liquid mercury reached this surface on one side and the mercury
vapor on the other without change of density on either side, then F2(i) will represent
the amount of water in the vicinity of this surface, per unit of surface, above that which
there would be, if the water- vapor just reached the surface without change of density,
and this quantity (which we may call the quantity of water condensed upon the surface
of the mercury) will be determined by the equation
do-
(In this differential coefficient as well as the following, the temperature is supposed to
remain constant and the surface of discontinuity plane. Practically, the latter condition
may be regarded as fulfilled in the case of any ordinary curvatures. )
If the pressure in the mixed vapors conforms to the law of Dalton (see pp. 155, 157),
we shall have for constant temperature
where pz denotes the part of the pressure in the vapor due to the water- vapor, and y2
the density of the water- vapor. Hence we obtain
d<r
For temperatures below 100° centigrade, this will certainly be accurate, since the
pressure due to the vapor of mercury may be neglected.
The value of <r for p2=0 and the temperature of 20° centigrade must be nearly the
same as the superficial tension of mercury in contact with air, or 55*03 grammes per
linear meter according to Quincke (Pogg. Ann., Bd. 139, p. 27). The value of <r at
the same temperature, when the condensed water begins to have the properties of water
236 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
The same physical relations may of course be deduced without
giving up the use of the surface of tension as a dividing surface, but
the formulae which express them will be less simple. If we make
t, /z3, //4, etc., constant, we have by (98) and (508)
where we may suppose I\ and F2 to be determined with reference
to the surface of tension. Then, if dp' — dp",
and
t rr
Ct/OT == 1. i - 7 ~/, CvlLn *™~ JL nC(/Un*
yi-yi
That is,
(£-) =-r2 + ri4^X;. (515)
\afJ.2/p' -p"t t, M3, M4> etc. Vi Vi
p
The reader will observe that — -, — - — „ represents the distance between
7i -Via
the surface of tension and that dividing surface which would make
I\ = 0 ; the second number of the last equation is therefore equivalent
to -r2(1).
If any component substance has the same density in the two homo-
geneous masses separated by a plane surface of discontinuity, the
value of the superficial density for that component is independent
of the position of the dividing surface. In this case alone we may
derive the value of the superficial density of a component with
reference to the surface of tension from the fundamental equation for
plane surfaces alone. Thus in the last equation, when y2' = y2", the
second member will reduce to — F2. It will be observed that to
in mass, will be equal to the sum of the superficial tensions of mercury in contact with
water and of water in contact with its own vapor. This will be, according to the same
authority, 42*58 + 8 "25, or 50 '83 grammes per meter, if we neglect the difference of the
tensions of water with its vapor and water with air. As p2, therefore, increases from
zero to 236400 grammes per square meter (when water begins to be condensed in mass),
<r diminishes from about 55*03 to about 50*83 grammes per linear meter. If the general
course of the values of a for intermediate values of p2 were determined by experiment, we
could easily form an approximate estimate of the values of the superficial density F
for different pressures less than that of saturated vapor. It will be observed that the
determination of the superficial density does not by any means depend upon inap-
preciable differences of superficial tension. The greatest difficulty in the determination
would doubtless be that of distinguishing between the diminution of superficial tension
due to the water and that due to other substances which might accidentally be present.
Such determinations are of considerable practical importance on account of the use of
mercury in measurements of the specific gravity of vapors.
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 237
make p'—p", t, yu3, //4, etc. constant is in this case equivalent to making
t, fjLl} /*3, /z4, etc. constant.
Substantially the same is true of the superficial density of entropy
or of energy, when either of these has the same density in the two
homogeneous masses.*
Concerning the Stability of Surfaces of Discontinuity between Fluid
Masses.
We shall first consider the stability of a film separating homo-
geneous masses with respect to changes in its nature, while its position
and the nature of the homogeneous masses are not altered. For this
purpose, it will be convenient to suppose that the homogeneous masses
are very large, and thoroughly stable with respect to the possible
formation of any different homogeneous masses out of their com-
ponents, and that the surface of discontinuity is plane and uniform.
Let us distinguish the quantities which relate to the actual com-
ponents of one or both of the homogeneous masses by the suffixes a, &,
etc., and those which relate to components which are found only at
the surface of discontinuity by the suffixes g) h) etc., and consider the
variation of the energy of the whole system in consequence of a given
change in the nature of a small part of the surface of discontinuity,
while the entropy of the whole system and the total quantities of the
several components remain constant, as well as the volume of each of
the homogeneous masses, as determined by the surface of tension.
This small part of the surface of discontinuity in its changed state
is supposed to be still uniform in nature, and such as may subsist
in equilibrium between the given homogeneous masses, which will
evidently not be sensibly altered in nature or thermodynamic state.
The remainder of the surface of discontinuity is also supposed to
* With respect to questions which concern only the form of surfaces of discontinuity,
such precision as we have employed in regard to the position of the dividing surface
is evidently quite unnecessary. This precision has not been used for the sake of the
mechanical part of the problem, which does not require the surface to be defined with
greater nicety than we can employ in our observations, but in order to give determinate
values to the superficial densities of energy, entropy, and the component substances,
which quantities, as has been seen, play an important part in the relations between
the tension of a surface of discontinuity, and the composition of the masses which it
separates.
The product <rs of the superficial tension and the area of the surface, may be regarded
as the available energy due to the surface in a system in which the temperature and
the potentials ftj , /*2, etc. — or the differences of these potentials and the gravitational
potential (see page 148) when the system is subject to gravity — are maintained sensibly
constant. The value of <r, as well as that of «, is sensibly independent of the precise
position which we may assign to the dividing surface (so long as this is sensibly coin-
cident with the surface of discontinuity), but es, the superficial density of energy, as the
term is used in this paper, like the superficial densities of entropy and of the component
substances, requires a more precise localization of the dividing surface.
238 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
remain uniform, and on account of its infinitely greater size to be
infinitely less altered in its nature than the first part. Let Ae8 denote
the increment of the superficial energy of this first part, A^8, Am8,
Am?, etc., Am8, Am8, etc., the increments of its superficial entropy
and of the quantities of the components which we regard as belonging
to the surface. The increments of entropy and of the various com-
ponents which the rest of the system receive will be expressed by
— A;/8, —Am8, — Am8, etc., —Am8, — Am?, etc.,
and the consequent increment of energy will be by (12) and (501)
- 1 A;/8 - yua Am8 - fjLb Am? - etc. - fig Am8 - jmh Amf - etc.
Hence the total increment of energy in the whole system will be
Ae8 - 1 A*?8 - fJLa Am8 - [j.b Am? - etc."
If the value of this expression is necessarily positive, for finite
changes as well as infinitesimal in the nature of the part of the film
to which Ae8, etc. relate,* the increment of energy of the whole
system will be positive for any possible changes in the nature of the
film, and the film will be stable, at least with respect to changes in
its nature, as distinguished from its position. For, if we write
De8, D^8, Dm8, Dm?, etc., Dm8, Dmf, etc.,
for the energy, etc. of any element of the surface of discontinuity, we
have from the supposition just made
A De8 — t A Dif — fjia A Dm8, — fib ADm? — etc.
— ju.g ADm8 — fjih A Dm8 — etc. > 0 ; (517)
and integrating for the whole surface, since
A/Dm8 = 0, A/Dm8 = 0, etc.,
we have
A/De8 - 1 A/D^8 - fjia A/Dm8 - fa A/Dm? - etc. > 0. (518)
Now A/Djy8 is the increment of the entropy of the whole surface,
and — A/D?/8 is therefore the increment of the entropy of the two
homogeneous masses. In like manner, —A/Dm8, —A/Dm?, etc.,
are the increments of the, quantities of the components in these
masses. The expression
- 1 A/D>?8 - fia A/Dm8 - pb A/Dm? - etc.
denotes therefore, according to equation (12), the increment of energy
of the two homogeneous masses, and since A/De8 denotes the
*In the case of infinitesimal changes in the nature of the film, the sign A must be
interpreted, as elsewhere in this paper, without neglect of infinitesimals of the higher
orders. Otherwise, by equation (501), the above expression would have the value zero.
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 239
increment of energy of the surface, the above condition expresses
that the increment of the total energy of the system is positive.
That we have only considered the possible formation of such films as
are capable of existing in equilibrium between the given homogeneous
masses can not invalidate the conclusion in regard to the stability of
the film, for in considering whether any state of the system will have
less energy than the given state, we need only consider the state of
least energy, which is necessarily one of equilibrium.
If the expression (516) is capable of a negative value for an
infinitesimal change in the nature of the part of the film to which
the symbols relate, the film is obviously unstable.
If the expression is capable of a negative value, but only for finite
and not for infinitesimal changes in the nature of this part of the
film, the film is practically unstable* i.e., if such a change were
made in a small part of the film, the disturbance would tend to
increase. But it might be necessary that the initial disturbance
should also have a finite magnitude in respect to the extent of
surface in which it occurs ; for we cannot suppose that the thermo-
dynamic relations of an infinitesimal part of a surface of discontinuity
are independent of the adjacent parts. On the other hand, the
changes which we have been considering are such that every part
of the film remains in equilibrium with the homogeneous masses
on each side ; and if the energy of the system can be diminished by
a finite change satisfying this condition, it may perhaps be capable
of diminution by an infinitesimal change which does not satisfy the
same condition. We must therefore leave it undetermined whether
the film, which in this case is practically unstable, is or is not
unstable in the strict mathematical sense of the term.
Let us consider more particularly the condition of practical stability,
in which we need not distinguish between finite and infinitesimal
changes. To determine whether the expression (516) is capable of a
negative value, we need only consider the least value of which it is
capable. Let us write it in the fuller form
e8" - e8' - t(f - f) - f^ (mf - mf) - /*6(mf - mf) - etc. \ _,
- Xr(mf - m?') - /4Of - wf) - etc.,/
where the single and double accents distinguish the quantities which
relate to the first and second states of the film, the letters without
accents denoting those quantities which have the same value in both
states. The differential of this expression when the quantities distin-
guished by double accents are alone considered variable, and the area
of the surface is constant, will reduce by (501) to the form
*With respect to the sense in which this term is used, compare page 79.
240 EQTJILIBKIUM OF HETEROGENEOUS SUBSTANCES.
To make this incapable of a negative value, we must have
fJLg = fJ.'g, unless mf = 0,
/*;=/4, unless mf = 0.
In virtue of these relations and by equation (502), the expression
(519), i.e., (516), will reduce to
a-" s — or' s,
which will be positive or negative according as
<r"-<r' (520)
is positive or negative.
That is, if the tension of the film is less than that of any other film
of the same components which can exist between the same homo-
geneous masses (which has therefore the same values of t, /*a, ju.b, etc.),
and which moreover has the same values of the potentials /mg, fa, etc.,
so far as it contains the substances to which these relate, then the
first film will be stable. But the film will be practically unstable,
if any other such film has a less tension. (Compare the expression
(141), by which the practical stability of homogeneous masses is
tested.)
It is, however, evidently necessary for the stability of the surface
of discontinuity with respect to deformation, that the value of the
superficial tension should be positive. Moreover, since we have by
(502) for the surface of discontinuity
es - trf - jULam* - fjibmf - etc. - /*,mj - //7tm^ - etc. = a-s, 4
and by (93) for the two homogeneous masses
e' - trf +pv' - fiama' - juibmb - etc. = 0,
e" - tif +pv" - nama" - fjibmbrf - etc. = 0,
if we denote by
e, ??, v, ma, mb) etc., mgt mh, etc.,
the total energy, etc. of a composite mass consisting of two such
homogeneous masses divided by such a surface of discontinuity, we
shall have by addition of these equations
€ — tr\ +pv — fj.ama — /ULbmb — etc. — fjLgmff — jULhmh — etc. = crs.
Now if the value of a- is negative, the value of the first member of
this equation will decrease as s increases, and may therefore be
decreased by making the mass to consist of thin alternate strata of
the two kinds of homogeneous masses which we are considering.
There will be no limit to the decrease which is thus possible with a
given value of v, so long as the equation is applicable, i.e., so long
as the strata have the properties of similar bodies in mass. But it
EQUILIBKIUM OF HETEROGENEOUS SUBSTANCES. 241
may easily be shown (as in a similar case on pages 77, 78) that
when the values of
t, P> t*a> ^6, etc., pgt //A, etc.,
are regarded as fixed, being determined by the surface of discon-
tinuity in question, and the values of
e, r\, ma, mb) etc., mg> mh, etc.,
are variable and may be determined by any body having the given
volume v, the first member of this equation cannot have an infinite
negative value, and must therefore have a least possible value, which
will be negative, if any value is negative, that is, if <r is negative.
The body determining e, 77, etc. which will give this least value
to this expression will evidently be sensibly homogeneous. With
respect to the formation of such a body, the system consisting of the
two homogeneous masses and the surface of discontinuity with the
negative tension is by (53) (see also page 79) at least practically
unstable, if the surface of discontinuity is very large, so that it can
afford the requisite material without sensible alteration of the values
of the potentials. (This limitation disappears, if all the component
substances are found in the homogeneous masses.) Therefore, in a
system satisfying the conditions of practical stability with respect to
the possible formation of all kinds of homogeneous masses, negative
tensions of the surfaces of discontinuity are necessarily excluded.
Let us now consider the condition which we obtain by applying
(516) to infinitesimal changes. The expression may be expanded as
before to the form (519), and then reduced by equation (502) to the
form '
That the value of this expression shall be positive when the quanti-
ties are determined by two films which differ infinitely little is a
necessary condition of the stability of the film to which the single
accents relate. But if one film is stable, the other will in general be
so too, and the distinction between the films with respect to stability
is of importance only at the limits of stability. If all films for all
values of /mff, /jih, etc. are stable, or all within certain limits, it is
evident that the value of the expression must be positive when the
quantities are determined by any two infinitesimally different films
within the same limits. For such collective determinations of stability
the condition may be written
— sAo- — m^A/Zj, — ml&/uLh — etc.>0,
or
Ao-<-rffA^-rftA//A-etc. (521)
On comparison of this formula with (508), it appears that within the
limits of stability the second and higher differential coefficients of the
G.I.
242 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
tension considered as a function of the potentials for the substances
which are found only at the surface of discontinuity (the potentials
for the substances found in the homogeneous masses and the tempera-
ture being regarded as constant) satisfy the conditions which would
make the tension a maximum if the necessary conditions relative to
the first differential coefficients were fulfilled.
In the foregoing discussion of stability, the surface of discontinuity
is supposed plane. In this case, as the tension is supposed positive,
there can be no tendency to a change of form of the surface. We
now pass to the consideration of changes consisting in or connected
with motion and change of form of the surface of tension, which we
shall at first suppose to be and to remain spherical and uniform
throughout.
In order that the equilibrium of a spherical mass entirely sur-
rounded by an indefinitely large mass of different nature shall be
neutral with respect to changes in the value of r, the radius of the
sphere, it is evidently necessary that equation (500), which in this
case may be written
9« — win' f}"\ ^P»99>\
•~cr — / \T: /^ /' \<j££i
as well as the other conditions of equilibrium, shall continue to hold
true for varying values of r. Hence, for a state of equilibrium which
is on the limit between stability and instability, it is necessary that
the equation
2da- = (pf -p") dr+r dp'
shall be satisfied, when the relations between da-, dp', arid dr are
determined from the fundamental equations on the supposition that
the conditions of equilibrium relating to temperature and the poten-
tials remain satisfied. (The differential coefficients in the equations
which follow are to be determined on this supposition.) Moreover, if
i.e., if the pressure of the interior mass increases less rapidly (or
decreases more rapidly) with increasing radius than is necessary to
preserve neutral equilibrium, the equilibrium is stable. But if
<524>
the equilibrium is unstable. In the remaining case, when
farther conditions are of course necessary to determine absolutely
whether the equilibrium is stable or unstable, but in general the
EQUILIBRIUM, OF HETEROGENEOUS SUBSTANCES. 243
equilibrium will be stable in respect to change in one direction and
unstable in respect to change in the opposite direction, and is therefore
to be considered unstable. In general, therefore, we may call (523)
the condition of stability.
When the interior mass and the surface of discontinuity are formed
entirely of substances which are components of the external mass, p'
and cr cannot vary, and condition (524) being satisfied the equilibrium
is unstable.
But if either the interior homogeneous mass or the surface of dis-
continuity contains substances which are not components of the
enveloping mass, the equilibrium may be stable. If there is but one
such substance, and we denote its densities and potential by y\, Yv
and juLlt the condition of stability (523) will reduce to the form
or, by (98) and (508),
(526)
In these equations and in all which follow in the discussion of this
case, the temperature and the potentials ju.2> /*3, etc. are to be regarded
as constant. But
which represents the total quantity of the component specified by the
suffix, must be constant. It is evidently equal to
Dividing by 4?r and differentiating, we obtain
(r*yi' + ^lydr +4** dyi'+r2 eO\ = 0,
or, since yx' and I\ are functions of JULV
0. (527)
By means of this equation, the condition of stability is brought to
the form
»"-
3
If we eliminate r by equation (522), we have
VlL+Ii)2
1 dT>l- (529)
•H
2o- a/*!
If p' and o- are known in terms of t, fa, //2, etc., we may express the
first member of this condition in terms of the same variables and p".
244 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
This will enable us to determine, for any given state of the external
mass, the values of fa which will make the equilibrium stable or
unstable.
If the component to which y/ and Tl relate is found only at the
surface of discontinuity, the condition of stability reduces to
- (530)
cr -n
bmce 1 1 = —
we may also write
I\ da- 1 dloga- 1
~^W< ~2' ' dlogT^ ~2'
dT
Again, if I\ = 0 and -j-1 = 0, the condition of stability reduces to
(532)
P -P
«. • /
Since y, =
we may also write
' or - (533)
' 3"
When r is large, this will be a close approximation for any values of
I\, unless y/ is very small. The two special conditions (531) and
(533) might be derived from very elementary considerations.
Similar conditions of stability may be found when there are more
substances than one in the inner mass or the surface of discontinuity,
which are not components of the enveloping mass. In this case, we
have instead of (526) a condition of the form
Jl+(ry2' + 2r2)^+etc.<^"-p', (534)
from which -^P, -&, etc. may be eliminated by means of equations
derived from the conditions that
yiV+I^s, y2V+r2s, etc.
must be constant.
Nearly the same method may be applied to the following problem.
Two different homogeneous fluids are separated by a diaphragm
having a circular orifice, their volumes being invariable except by
the motion of the surface of discontinuity, which adheres to the edge
of the orifice ; — to determine the stability or instability of this surface
when in equilibrium.
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 245
The condition of stability derived from (522) may in this case be
written
where the quantities relating to the concave side of the surface of
tension are distinguished by a single accent.
If both the masses are infinitely large, or if one which contains all
the components of the system is infinitely large, p' —p" and o- will
be constant, and the condition reduces to
dr
;r-7
dv
The equilibrium will therefore be stable or unstable according as the
surface of tension is less or greater than a hemisphere.
To return to the general problem : — if we denote by x the part of
the axis of the circular orifice intercepted between the center of the
orifice and the surface of tension, by R the radius of the orifice, and
by V the value of vf when the surface of tension is plane, we shall
have the geometrical relations
and v'= F'
By differentiation we obtain
(r — x)dx + x dr — 0,
and dv' = irx2 dr + (Sirrx — TTXZ) dx ;
whence (r — x)dvf = — irrx2 dr. (536)
By means of this relation, the condition of stability may be reduced
to the form
^_^1_? *«L<(rf-v»\ r"x (537)
dv' dv' rdv'<(P P)-jrrW
Let us now suppose that the temperature and all the potentials
except one, JULV are to be regarded as constant. This will be the case
when one of the homogeneous masses is very large and contains all
the components of the system except one, or when both these masses
are very large and there is a single substance at the surface of dis-
continuity which is not a component of either ; also when the whole
system contains but a single component, and is exposed to a constant
temperature at its surface. Condition (537) will reduce by (98) and
(508) to the form
(538)
246 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
But y i v' -}- y , "v" -f- 17, 8
(the total quantity of the component specified by the suffix) must be
constant ; therefore, since
2
dv" — — dv', and ds = - dv'
r
By this equation, the condition of stability is brought to the form
x — r
When the substance specified by the suffix is a component of either
of the homogeneous masses, the terms - — and s -r-± may generally
be neglected. When it is not a component of either, the terms y/,
Vi"> V'T» v" j may of course be cancelled, but we must not
j
CvjJL-,
apply the formula to cases in which the substance spreads over the
diaphragm separating the homogeneous masses.
In the cases just discussed, the problem of the stability of certain
surfaces of tension has been solved by considering the case of neutral
equilibrium, — a condition of neutral equilibrium affording the equation
of the limit of stability. This method probably leads as directly as
any to the result, when that consists in the determination4 of the
value of a certain quantity at the limit of stability, or of the relation
which exists at that limit between certain quantities specifying the
state of the system. But problems of a more general character may
require a more general treatment.
Let it be required to ascertain the stability or instability of a fluid
system in a given state of equilibrium with respect to motion of the
surfaces of tension and accompanying changes. It is supposed that
the conditions of internal stability for the separate homogeneous
masses are satisfied, as well as those conditions of stability for the
surfaces of discontinuity which relate to small portions of these
surfaces with the adjacent masses. (The conditions of stability which
are here supposed to be satisfied have been already discussed in part
and will be farther discussed hereafter.) The fundamental equations
for all the masses and surfaces occurring in the system are supposed
to be known. In applying the general criteria of stability which are
given on page 57, we encounter the following difficulty.
The question of the stability of the system is to be determined by
the consideration of states of the system which are slightly varied
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 247
from that of which the stability is in question. These varied states
of the system are not in general states of equilibrium, and the
relations expressed by the fundamental equations may not hold true
of them. More than this, — if we attempt to describe a varied state of
the system by varied values of the quantities which describe the
initial state, if these varied values are such as are inconsistent with
equilibrium, they may fail to determine with precision any state of
the system. Thus, when the phases of two contiguous homogeneous
masses are specified, if these phases are such as satisfy all the
conditions of equilibrium, the nature of the surface of discontinuity
(if without additional components) is entirely determined ; but if the
phases do not satisfy all the conditions of equilibrium, the nature of
the surface of discontinuity is not only undetermined, but incapable
of determination by specified values of such quantities as we have
employed to express the nature of surfaces of discontinuity in
equilibrium. For example, if the temperatures in contiguous homo-.
geneous masses are different, we cannot specify the thermal state
of the surface of discontinuity by assigning to it any particular
temperature. It would be necessary to give the law by which the
temperature passes over from one value to the other. And if this
were given, we could make no use of it in the determination of other
quantities, unless the rate of change of the temperature were so
gradual that at every point we could regard the thermodynamic state
as unaffected by the change of temperature in its vicinity. It is true
that we are also ignorant in respect to surfaces of discontinuity in
equilibrium of the law of change of those quantities which are
different in the two phases in contact, such as the densities of the
components, but this, although unknown to us, is entirely determined
by the nature of the phases in contact, so that no vagueness is
occasioned in the definition of any of the quantities which we have
occasion to use with reference to such surfaces of discontinuity.
It may be observed that we have established certain differential
equations, especially (497), in which only the initial state is necessarily
one of equilibrium. Such equations may be regarded as establishing
certain properties of states bordering upon those of equilibrium. But
these are properties which hold true only when we disregard quantities
proportional to the square of those which express the degree of
variation of the system from equilibrium. Such equations are there-
fore sufficient for the determination of the conditions of equilibrium,
but not sufficient for the determination of the conditions of stability.
We may, however, use the following method to decide the question
of stability in such a case as has been described.
Beside the real system of which the stability is in question, it will
be convenient to conceive of another system, to which we shall
248 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
attribute in its initial state the same homogeneous masses and surfaces
of discontinuity which belong to the real system. We shall also
suppose that the homogeneous masses and surfaces of discontinuity of
this system, which we may call the imaginary system, have the same
fundamental equations as those of the real system. But the imaginary
system is to differ from the real in that the variations of its state are
limited to such as do not violate the conditions of equilibrium relating
to temperature and the potentials, and that the fundamental equations
of the surfaces of discontinuity hold true for these varied states,
although the condition of equilibrium expressed by equation (500)
may not be satisfied.
Before proceeding farther, we must decide whether we are to
examine the question of stability under the condition of a constant
external temperature, or under the condition of no transmission of
heat to or from external bodies, and in general, to what external
influences we are to regard the system as subject. It will be con-
venient to suppose that the exterior of the system is fixed, and that
neither matter nor heat can be transmitted through it. Other cases
may easily be reduced to this, or treated in a manner entirely
analogous.
Now if the real system in the given state is unstable, there must be
some slightly varied state in which the energy is less, but the entropy
and the quantities of the components the same as in the given state,
and the exterior of the system unvaried. But it may easily be shown
that the given state of the system may be made stable by constraining
the surfaces of discontinuity to pass through certain fixed lines situated
in the unvaried surfaces. Hence, if the surfaces of discontinuity are
constrained to pass through corresponding fixed lines in the surfaces
of discontinuity belonging to the varied state just mentioned, there
must be a state of stable equilibrium for the system thus constrained
which will differ infinitely little from the given state of the system,
the stability of which is in question, and will have the same
entropy, quantities of components, and exterior, but less energy.
The imaginary system will have a similar state, since the real and
imaginary systems do not differ in respect to those states which satisfy
all the conditions of equilibrium for each surface of discontinuity.
That is, the imaginary system has a state, differing infinitely little
from the given state, and with the same entropy, quantities of
components, and exterior, but with less energy.
Conversely, if the imaginary system has such a state as that just
described, the real system will also have such a state. This may be
shown by fixing certain lines in the surfaces of discontinuity of the
imaginary system in its state of less energy and then making the
energy a minimum under the conditions. The state thus determined
EQUILIBKIUM OF HETEROGENEOUS SUBSTANCES. 249
will satisfy all the conditions of equilibrium for each surface of
discontinuity, and the real system will therefore have a corresponding
state, in which the entropy, quantities of components, and exterior
will be the same as in the given state, but the energy less.
We may therefore determine whether the given system is or is not
unstable, by applying the general criterion of instability (7) to the
imaginary system.
If the system is not unstable, the equilibrium is either neutral or
stable. Of course we can determine which of these is the case by
reference to the imaginary system, since the determination depends
upon states of equilibrium, in regard to which the real and imaginary
systems do not differ. We may therefore determine whether the
equilibrium of the given system is stable, neutral, or unstable, by
applying the criteria (3)-(7) to the imaginary system.
The result which we have obtained may be expressed as follows : —
In applying to a fluid system which is in equilibrium, and of which
all the small parts taken separately are stable, the criteria of stable,
neutral, and unstable equilibrium, we may regard the system as
under constraint to satisfy the conditions of equilibrium relating to
temperature and the potentials, and as satisfying the relations ex-
pressed by the fundamental equations for masses and surfaces, even
when the condition of equilibrium relating to pressure {equation (500)}
is not satisfied.
It follows immediately from this principle, in connection with
equations (501) and (86), that in a stable system each surface of
tension must be a surface of minimum area for constant values of the
volumes which it divides, when the other surfaces bounding these
volumes and the perimeter of the surface of tension are regarded as
fixed ; that in a system in neutral equilibrium each surface of tension
will have as small an area as it can receive by any slight variations
under the same limitations ; and that in seeking the remaining con-
ditions of stable or neutral equilibrium, when these are satisfied, it
is only necessary to consider such varied surfaces of tension as
have similar properties with reference to the varied volumes and
perimeters.
We may illustrate the method which has been described by apply-
ing it to a problem but slightly different from one already (pp. 244,
245) discussed by a different method. It is required to determine the
conditions of stability for a system in equilibrium, consisting of two
different homogeneous masses meeting at a surface of discontinuity,
the perimeter of which is invariable, as well as the exterior of the
whole system, which is also impermeable to heat.
To determine what is necessary for stability in addition to the
condition of minimum area for the surface of tension, we need only
250
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
consider those varied surfaces of tension which satisfy the same con-
dition. We may therefore regard the surface of tension as determined
by v, the volume of one of the homogeneous masses. But the state
of the system would evidently be completely determined by the
position of the surface of tension and the temperature and potentials,
if the entropy and the quantities of the components were variable;
and therefore, since the entropy and the quantities of the components
are constant, the state of the system must be completely determined
by the position of the surface of tension. We may therefore regard
all the quantities relating to the system as functions of v', and the
condition of stability may be written
de 7 , , 1 d2e
&**+*-
where e denotes the total energy of the system. Now the conditions
of equilibrium require that
dv'~
Hence, the general condition of stability is that
T-75
dv2
(541)
Now if we write e', e", es for the energies of the two masses and of
the surface, we have by (86) and (501), since the total entropy and
the total quantities of the several components are constant,
de = de' + de" + de8 = -p'dv' -p"dv" + <rds,
or, since dv" = — dv',
de_
dv'
ds
Hence,
d2e _dp' dp" da- ds
dv7*' 'M+W^MM
d2s
(542)
(543)
and the condition of stability may be written
d2s dp' dp" da- ds
dv'2 dv' dv' dv'dv''
(544)
If we now simplify the problem by supposing, as in the similar
case on page 245, that we may disregard the variations of the
temperature and of all the potentials except one, the condition will
reduce to
70 t T ^ 1
(545)
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 251
The total quantity of the substance indicated by the suffix x is
Making this constant, we have
** (546)
The condition of equilibrium is thus reduced to the form
da \2
,dy'
-^
fj Q fl 2o
where -j—f and -^-7 are to be determined from the form of the surface
dv dv
of tension by purely geometrical considerations, and the other differ-
ential coefficients are to be determined from the fundamental equations
of the homogeneous masses and the surface of discontinuity. Condition
(540) may be easily deduced from this as a particular case.
The condition of stability with reference to motion of surfaces of
discontinuity admits of a very simple expression when we can treat
the temperature and potentials as constant. This will be the case
when one or more of the homogeneous masses, containing together
all the component substances, may be considered as indefinitely large,
the surfaces of discontinuity being finite. For if we write 2Ae for
the sum of the variations of the energies of the several homogeneous
masses, and 2Aes for the sum of the variations of the energies of the
several surfaces of discontinuity, the condition of stability may be
written
0, (548)
the total entropy and the total quantities of the several components
being constant. The variations to be considered are infinitesimal,
but the character A signifies, as elsewhere in this paper, that the
expression is to be interpreted without neglect of infinitesimals of the
higher orders. Since the temperature and potentials are sensibly
constant, the same will be true of the pressures and surface-tensions,
and by integration of (86) and (501) we may obtain for any homo-
geneous mass
Ae = t AT; —p A v + fa Amx + /z2 Am2 + etc.,
and for any surface of discontinuity
Aes = t A V3 + a- As -j- fa Am? + /*f Am2 + etc.
These equations will hold true of finite differences, when t, p, &, yu1?
JUL^, etc. are constant, and will therefore hold true of infinitesimal
differences, under the same limitations, without neglect of the
252 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
infinitesimals of the higher orders. By substitution of these values,
the condition of stability will reduce to the form
or 2(p Av) - 2 (<r As) < 0. (549)
That is, the sum of the products of the volumes of the masses by
their pressures, diminished by the sum of the products of the areas of
the surfaces of discontinuity by their tensions, must be a maximum.
This is a purely geometrical condition, since the pressures and tensions
are constant. This condition is of interest, because it is always
sufficient for stability with reference to motion of surfaces of discon-
tinuity. For any system may be reduced to the kind described by
putting certain parts of the system in communication (by means of
fine tubes if necessary) with large masses of the proper temperatures
and potentials. This may be done without introducing any new
movable surfaces of discontinuity. The condition (549) when applied
to the altered system is therefore the same as when applied to the
original system. But it is sufficient for the stability of the altered
system, and therefore sufficient for its stability if we diminish its
freedom by breaking the connection between the original system and
the additional parts, and therefore sufficient for the stability of the
original system.
On the Possibility of the Formation of a Fluid of different Phase
within any Homogeneous Fluid.
The study of surfaces of discontinuity throws considerable light
upon the subject of the stability of such homogeneous fluid masses
as have a less pressure than others formed of the same components
(or some of them) and having the same temperature and the same
potentials for their actual components.*
In considering this subject, we must first of all inquire how far our
method of treating surfaces of discontinuity is applicable to cases
in which the radii of curvature of the surfaces are of insensible
magnitude. That it should not be applied to such cases without
limitation is evident from the consideration that we have neglected
the term ^(Ol — C^)8(cl — c^) in equation (494) on account of the
magnitude of the radii of curvature compared with the thickness
of the non-homogeneous film. (See page 228.) When, however, only
spherical masses are considered, this term will always disappear, since
C1 and 02 will necessarily be equal.
*See page 104, where the term stable is used (as indicated on page 103) in a less
strict sense than in the discussion which here follows.
EQUILIBEIUM OF HETEROGENEOUS SUBSTANCES. 253
Again, the surfaces of discontinuity have been regarded as separating
homogeneous masses. But we may easily conceive that a globular
mass (surrounded by a large homogeneous mass of different nature)
may be so small that no part of it will be homogeneous, and that
even at its center the matter cannot be regarded as having any
phase of matter in mass. This, however, will cause no difficulty, if
we regard the phase of the interior mass as determined by the same
relations to the exterior mass as in other cases. Beside the phase of
the exterior mass, there will always be another phase having the
same temperature and potentials, but of the general nature of the
small globule which is surrounded by that mass and in equilibrium
with it. This phase is completely determined by the system con-
sidered, and in general entirely stable and perfectly capable of realiza-
tion in mass, although not such that the exterior mass could exist
in contact with it at a plane surface. This is the phase which we
are to attribute to the mass which we conceive as existing within the
dividing surface.*
With this understanding with regard to the phase of the fictitious
interior mass, there will be no ambiguity in the meaning of any of
the symbols which we have employed, when applied to cases in which
the surface of discontinuity is spherical, however small the radius
may be. Nor will the demonstration of the general theorems require
any material modification. The dividing surface which determines
the value of e9, if, mf, mf , etc. is as in other cases to be placed so as
to make the term K^i + ^2)^(ci+c2) in equation (494) vanish, i.e., so
as to make equation (497) valid. It has been shown on pages 225-227
that when thus placed it will sensibly coincide with the physical
surface of discontinuity, when this consists of a non-homogeneous
film separating homogeneous masses, and having radii of curvature
which are large compared with its thickness. But in regard to
globular masses too small for this theorem to have any application, it
will be worth while to examine how far we may be certain that the
radius of the dividing surface will have a real and positive value,
since it is only then that our method will have any natural application.
The value of the radius of the dividing surface, supposed spherical,
of any globule in equilibrium with a surrounding homogeneous fluid
may be most easily obtained by eliminating a- from equations (500)
and (502), which have been derived from (497), and contain the radius
implicitly. If we write r for this radius, equation (500) may be written
2(r = (p'-p")r, (550)
* For example, in applying our formulae to a microscopic globule of water in steam,
by the density or pressure of the interior mass we should understand, not the actual
density or pressure at the center of the globule, but the density of liquid water (in
large quantities) which has the temperature and potential of the steam.
254
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
the single and double accents referring respectively to the interior
and exterior masses. If we write [e], [77], [mj, [m2], etc., for the
excess of the total energy, entropy, etc., in and about the globular
mass above what would be in the same space if it were uniformly
filled with matter of the phase of the exterior mass, we shall have
necessarily with reference to the whole dividing surface
e8 = [6] - t/(6v' - O> f = W - t/fthr' - */X
= M-'y/(y2/-A etc.,
where ev'> €v"> nv> *7v"> y\> y"> e^c. denote, in accordance with our
usage elsewhere, the volume-densities of energy, of entropy, and of
the various components, in the two homogeneous masses. We may
thus obtain from equation (502)
as = [e] - t/(6v' - ev") - 1 M + fc/fov' - */)
- A*I W + /*X(yi' - y/') - /*2[>v] + A^'fo' - y2") - etc. (551)
But by (93),
p' = - ev' + ^v' + |£iyi' + ^2y2' + etc.,
Let us also write for brevity
W= [e] — t\ri\ — /^[mj — //2[m2] "~ e^c- (552)
(It will be observed that the value of W is entirely determined by
the nature of the physical system considered, and that the notion of
the dividing surface does not in any way enter into its definition.)
We shall then have
<rs = W+ v(p' -p"), (553)
or, substituting for s and v' their values in terms of r,
and eliminating <r by (550),
-p")=W, (555)
i* • —
If we eliminate r instead of <r, we have
ar =
167T
(556)
(557)
(558)
Now, if we first suppose the difference of the pressures in the homo-
geneous masses to be very small, so that the surface of discontinuity
is nearly plane, since without any important loss of generality we
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 255
may regard a- as positive (for if & is not positive when p' =£>", the
surface when plane would not be stable in regard to position, as
it certainly is, in every actual case, when the proper conditions are
fulfilled with respect to its perimeter), we see by (550) that the
pressure in the interior mass must be the greater ; i.e., we may regard
a; p'—p", and r as all positive. By (555), the value of W will also
be positive. But it is evident from equation (552), which defines W,
that the value of this quantity is necessarily real, in any possible case
of equilibrium, and can only become infinite when r becomes infinite
and p'—p". Hence, by (556) and (558), as p'—p" increases from very
small values, W, r, and a- have single, real, and positive values until
they simultaneously reach the value zero. Within this limit, our
method is evidently applicable ; beyond this limit, if such exist, it will
hardly be profitable to seek to interpret the equations. But it must
be remembered that the vanishing of the radius of the somewhat
arbitrarily determined dividing surface may not necessarily involve
the vanishing of the physical heterogeneity. It is evident, however
(see pp. 225-227), that the globule must become insensible in magni-
tude before r can vanish.
It may easily be shown that the quantity denoted by W is the
work which would be required to form (by a reversible process) the
heterogeneous globule in the interior of a very large mass having
initially the uniform phase of the exterior mass. For this work is
equal to the increment of energy of the system when the globule is
formed without change of the entropy or volume of the whole system
or of the quantities of the several components. Now [;/], [wj, [m2],
etc. denote the increments of entropy and of the components in the
space where the globule is formed. Hence these quantities with
the negative sign will be equal to the increments of entropy and
of the components in the rest of the system. And hence, by
equation (86), ,r n r n r n
- 1 M ~ A*i OJ - 02 M - etc-
will denote the increment of energy in all the system except where
the globule is formed. But [e] denotes the increment of energy in
that part of the system. Therefore, by (552), W denotes the total
increment of energy in the circumstances supposed, or the work
required for the formation of the globule.
The conclusions which may be drawn from these considerations
with respect to the stability of the homogeneous mass of the pressure
p" (supposed less than p', the pressure belonging to a different phase
of the same temperature and potentials) are very obvious. Within
those limits within which the method used has been justified, the
mass in question must be regarded as in strictness stable with respect
to the growth of a globule of the kind considered, since W, the work
256 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
required for the formation of such a globule of a certain size (viz.,
that which would be in equilibrium with the surrounding mass), will
always be positive. Nor can smaller globules be formed, for they can
neither be in equilibrium with the surrounding mass, being too small,
nor grow to the size of that to which W relates. If, however, by
any external agency such a globular mass (of the size necessary for
equilibrium) were formed, the equilibrium has already (page 243)
been shown to be unstable, and with the least excess in size, the
interior mass would tend to increase without limit except that
depending on the magnitude of the exterior mass. We may therefore
regard the quantity W as affording a kind of measure of the stability
of the phase to which p" relates. In equation (557) the value of W
is given in terms of cr and p' —p". If the three fundamental equa-
tions which give cr, p', and p" in terms of the temperature and the
potentials were known, we might regard the stability ( W) as known
in terms of the same variables. It will be observed that when^/=jp"
the value of W is infinite. If p' — p" increases without greater
changes of the phases than are necessary for such increase, W will
vary at first very nearly inversely as the square of p' —p". If p' —p"
continues to increase, it may perhaps occur that W reaches the value
zero ; but until this occurs the phase is certainly stable with respect
to the kind of change considered. Another kind of change is con-
ceivable, which initially is small in degree but may be great in its
extent in space. Stability in this respect or stability in respect to
continuous changes of phase has already been discussed (see page
105), and its limits determined. These limits depend entirely upon
the fundamental equation of the homogeneous mass of which the
stability is in question. But with respect to the kind of changes
here considered, which are initially small in extent but great in
degree, it does not appear how we can fix the limits of stability with
the same precision. But it is safe to say that if there is such a limit
it must be at or beyond the limit at which <r vanishes. This latter
limit is determined entirely by the fundamental equation of the
surface of discontinuity between the phase of which the stability is
in question and that of which the possible formation is in question.
We have already seen that when a- vanishes, the radius of the
dividing surface and the work W vanish with it. If the fault in
the homogeneity of the mass vanishes at the same time (it evidently
cannot vanish sooner), the phase becomes unstable at this limit.
But if the fault in the homogeneity of the physical mass does not
vanish with r, or and W, — and no sufficient reason appears why
this should not be considered as the general case, — although the
amount of work necessary to upset the equilibrium of the phase
is infinitesimal, this is not enough to make the phase unstable.
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 257
It appears therefore that W is a somewhat one-sided measure of
stability.
It must be remembered in this connection that the fundamental
equation of a surface of discontinuity can hardly be regarded as
capable of experimental determination, except for plane surfaces (see
pp. 231-233), although the relation for spherical surfaces is in the
nature of things entirely determined, at least so far as the phases are
separately capable of existence. Yet the foregoing discussion yields
the following practical results. It has been shown that the real
stability of a phase extends in general beyond that limit (discussed
on pages 103-105), which may be called the limit of practical stability,
at which the phase can exist in contact with another at a plane
surface, and a formula has been deduced to express the degree of
stability in such cases as measured by the amount of work necessary
to upset the equilibrium of the phase when supposed to extend
indefinitely in space. It has also been shown to be entirely consistent
with the principles established that this stability should have limits,
and the manner in which the general equations would accommodate
themselves to this case has been pointed out.
By equation (553), which may be written
W=<rs-(p'-p")v', (559)
we see that the work W consists of two parts, of which one is always
positive, and is expressed by the product of the superficial tension
and the area of the surface of tension, and the other is always
negative, and is numerically equal to the product of the difference
of pressure by the volume of the interior mass. We may regard the
first part as expressing the work spent in forming the surface of
tension, and the second part the work gained in forming the interior
mass.* Moreover, the second of these quantities, if we neglect its
* To make the physical significance of the above more clear, we may suppose the two
processes to be performed separately in the following manner. We may suppose a large
mass of the same phase as that which has the volume v' to exist initially in the interior
of the other. Of course, it must be surrounded by a resisting envelop, on account of
the difference of the pressures. We may, however, suppose this envelop permeable
to all the component substances, although not of such properties that a mass can form
on the exterior like that within. We may allow the envelop to yield to the internal
pressure until its contents are increased by v' without materially affecting its superficial
area. If this be done sufficiently slowly, the phase of the mass within will remain
constant. (See page 84.) A homogeneous mass of the volume v' and of the desired
phase has thus been produced, and the work gained is evidently (p1 -p")v'.
Let us suppose that a small aperture is now opened and closed in the envelop so as
to let out exactly the volume v' of the mass within, the envelop being pressed, inwards
in another place so as to diminish its contents by this amount. During the extrusion of
the drop and until the orifice is entirely closed, the surface of the drop must adhere to
the edge of the orifice, but not elsewhere to the outside surface of the envelop. The
work done in forming the surface of the drop will evidently be <rs or %(p' -p")tf. Of
G. I. R
258 EQUILIBKIUM OF HETEROGENEOUS SUBSTANCES.
sign, is always equal to two-thirds of the first, as appears from
equation (550) and the geometrical relation v' = Jm We may there-
fore write
/>'• (560)
On the Possible Formation at the Surface where two different
Homogeneous Fluids meet of a Fluid of different Phase
from either.
Let A, B, and C be three different fluid phases of matter, which
satisfy all the conditions necessary for equilibrium when they meet
at plane surfaces. The components of A and B may be the same or
different, but C must have no components except such as belong to
A or B. Let us suppose masses of the phases A and B to be separated
by a very thin sheet of the phase C. This sheet will not necessarily
be plane, but the sum of its principal curvatures must be zero. We
may treat such a system as consisting simply of masses of the phases
A and B with a certain surface of discontinuity, for in our previous
discussion there has been nothing to limit the thickness or the nature
of the film separating homogeneous masses, except that its thickness
has generally been supposed to be small in comparison with its radii
of curvature. The value of the superficial tension for such a film
will be CTAC + CTBCJ if we denote by these symbols the tensions of the
surfaces of contact of the phases A and C, and B and C, respectively.
This not only appears from evident mechanical considerations, but
may also be easily verified by equations (502) and (93), the first of
which may be regarded as defining the quantity or. This value will
not be affected by diminishing the thickness of the film, until the
limit is reached at which the interior of the film ceases to have the
properties of matter in mass. Now if c7Ao + o"BO ig greater than <TAB
the tension of the ordinary surface between A and B, such a film will
be at least practically unstable. (See page 240.) We cannot suppose
that (TAB > 0"Ac+<*"Bc> ^or tins would make the ordinary surface between
A and B unstable and difficult to realize. If crAB = 0"Ac + 0"Bc> we may
assume, in general, that this relation is not accidental, and that the
ordinary surface of contact for A and B is of the kind which we have
described.
Let us now suppose the phases A and B to vary, so as still to
satisfy the conditions of equilibrium at plane contact, but so that the
pressure of the phase C determined by the temperature and potentials
this work, the amount (pr —p")v' will be expended in pressing the envelop inward, and
the rest in opening and closing the orifice. Both the opening and the closing will be
resisted by the capillary tension. If the orifice is circular, it must have, when widest
open, the radius determined by equation (550).
EQUILIBKIUM OF HETEROGENEOUS SUBSTANCES. 259
of A and B shall become less than the pressure of A and B. A system
consisting of the phases A and B will be entirely stable with respect
to the formation of any phase like C. (This case is not quite identical
with that considered on page 104, since the system in question con-
tains two different phases, but the principles involved are entirely
the same.)
With respect to variations of the phases A and B in the opposite
direction we must consider two cases separately. It will be con-
venient to denote the pressures of the three phases by £>A, pB, pc, and
to regard these quantities as functions of the temperature and
potentials.
If 0-AB = <7AC + a-BC for values of the temperature and potentials which
make PA—PB—PC) it w^[ not be possible to alter the temperature and
potentials at the surface of contact of the phases A and B so that
PA~PB> an(i PC>PA> f°r the relation of the temperature and potentials
necessary for the equality of the three pressures will be preserved by
the increase of the mass of the phase C. Such variations of the phases
A and B might be brought about in separate masses, but if these
were brought into contact, there would be an immediate formation
of a mass of the phase C, with reduction of the phases of the adjacent
masses to such as satisfy the conditions of equilibrium with that
phase.
But if O-AB < 0"Ac + 0"Bc> we can vary the temperature and potentials
so that j9A=_pB, and pc > p&, and it will not be possible for a sheet of
the phase of C to form immediately, i.e., while the pressure of C is
sensibly equal to that of A and B ; for mechanical work equal to
o'Ac+o'Bc-'O'AB per unit of surface might be obtained by bringing the
system into its original condition, and therefore produced without
any external expenditure, unless it be that of heat at the temperature
of the system, which is evidently incapable of producing the work.
The stability of the system in respect to such a change must therefore
extend beyond the point where the pressure of C commences to be
greater than that of A and B. We arrive at the same result if we use
the expression (520) as a test of stability. Since this expression has
a finite positive value when the pressures of the phases are all equal,
the ordinary surface of discontinuity must be stable, and it must
require a finite change in the circumstances of the case to make it
become unstable.*
*It is true that such a case as we are now considering is formally excluded in the
discussion referred to, which relates to a plane surface, and in which the system is
supposed thoroughly stable • with respect to the possible formation of any different
homogeneous masses. Yet the reader will easily convince himself that the criterion
(520) is perfectly valid in this case with respect to the possible formation of a thin sheet
of the phase C, which, as we have seen, may be treated simply as a different kind of
surface of discontinuity.
260 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
In the preceding paragraph it is shown that the surface of contact
of phases A and B is stable under certain circumstances, with respect
to the formation of a thin sheet of the phase C. To complete the
demonstration of the stability of the surface with respect to the
formation of the phase C, it is necessary to show that this phase
cannot be formed at the surface in lentiform masses. This is the
more necessary, since it is in this manner, if at all, that the phase
is likely to be formed, for an incipient sheet of phase
C would evidently be unstable when CAB <0-Ao+0"Bc>
and would immediately break up into lentiform
masses.
It will be convenient to consider first a lentiform
mass of phase C in equilibrium between masses of
phases A and B which meet in a plane surface. Let
figure 10 represent a section of such a system through
the centers of the spherical surfaces, the mass of phase
A lying on the left of DEH'FG, and that of phase B
on the right of DEH"FG. Let the line joining the
centers cut the spherical surfaces in IT and H", and the
plane of the surface of contact of A and B in I. Let
the radii of EH'F and EH"F be denoted by r', r", and the segments
IH', IH", by x', x". Also let IE, the radius of the circle in
which the spherical surfaces intersect, be denoted by R. By a
suitable application of the general condition of equilibrium we may
easily obtain the equation
r -x'
r"-x
(561)
which signifies that the components parallel to EF of the tension
(TAG &nd <TBO are together equal to O-AB- If we denote by TFthe amount
of work which must be expended in order to form such a lentiform
mass as we are considering between masses of indefinite extent having
the phases A and B, we may write
W=M-N, (562)
where M denotes the work expended in replacing the surface between
A and B by the surfaces between A and C and B and C, and N
denotes the work gained in replacing the masses of phases A and B
by the mass of phase C. Then
-O-AB«AB> (563)
where sAc> SBO> SAB denote the areas of the three surfaces concerned;
and
JV= V'(pG -pA) + V"(p0 -pB), (564)
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 261
where V and V" denote the volumes of the masses of the phases
A and B which are replaced. Now by (500),
J»O-J»A-^, and Po-pe = ^>. (565)
We have also the geometrical relations
F'=f^'-^(r' -*'),!
V" = |*yi a" - %TrR*(r" - a"). J
By substitution we obtain
= -JTT (TAG rV - |7T^2 <TAO
— x
O-BO r' V -
OBC
and by (561),
Since
we may write
2-TrrV =
2?rr V = S
BO ,
= S
AB »
(567)
(568)
(569)
(The reader will observe that the ratio of M and N is the same as that
of the corresponding quantities in the case of the spherical mass
treated on pages 252-258.) We have therefore
^r=¥(o-AosAO + o-BCsBC — o*AB SAB)- (570)
This value is positive so long as
since SAC > SAB > and SBC>SAB-
But at the limit, when
we see by (561) that
and therefore
SAO = SAB > and SBC =
TF=0.
It should however be observed that in the immediate vicinity of
the circle in which the three surfaces of discontinuity intersect, the
physical state of each of these surfaces must be affected by the
vicinity of the others. We cannot, therefore, rely upon the formula
(570) except when the dimensions of the lentiform mass are of sensible
magnitude.
We may conclude that after we pass the limit at which p0 becomes
greater than pA and PB (supposed equal) lentiform masses of phase C
will not be formed until either O-AB = °"AC + O"BC> or Po—p± becomes so
great that the lentiform mass which would be in equilibrium is one
262 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
of insensible magnitude. {The diminution of the radii with increasing
values of p0 — pA is indicated by equation (565).} Hence, no mass of
phase C will be formed until one of these limits is reached. Although
the demonstration relates to a plane surface between A and B, the
result must be applicable whenever the radii of curvature have a
sensible magnitude, since the effect of such curvature may be dis-
regarded when the lentiform mass is sufficiently small.
The equilibrium of the lentiform mass of phase C is easily proved
to be unstable, so that the quantity W affords a kind of measure of
the stability of plane surfaces of contact of the phases A and B.*
Essentially the same principles apply to the more general problem
in which the phases A and B have moderately different pressures, so
that their surfaces of contact must be curved, but the radii of curva-
ture have a sensible magnitude.
In order that a thin film of the phase C may be in equilibrium
between masses of the phases A and B, the following equations must
be satisfied: — ,
where c^ and c2 denote the principal curvatures of the film, the
centers of positive curvature lying in the mass having the phase A.
Eliminating Cj + Cg, we have
(PA. -PC) = <TAC (Po -Pv)>
or po==BcA ACB. (571)
"
It is evident that if pc has a value greater than that determined by
this equation, such a film will develop into a larger mass ; if pc has a
less value, such a film will tend to diminish. Hence, when
the phases A and B have a stable surface of contact.
* If we represent phases by the position of points in such a manner that coexistent
phases (in the sense in which the term is used on page 96) are represented by the same
point, and allow ourselves, for brevity, to speak of the phases as having the positions of
the points by which they are represented, we may say that three coexistent phases are
situated where three series of pairs of coexistent phases meet or intersect. If the three
phases are all fluid, or when the effects of solidity may be disregarded, two cases are to
be distinguished. Either the three series of coexistent phases all intersect, — this is
when each of the three surface tensions is less than the sum of the two others, — or one
of the series terminates where the two others intersect, — this is where one surface
tension is equal to the sum of the others. The series of coexistent phases will be
represented by lines or surfaces, according as the phases have one or two independently
variable components. Similar relations exist when the number of components is greater,
except that they are not capable of geometrical representation without some limitation,
as that of constant temperature or pressure or certain constant potentials.
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 263
Again, if more than one kind of surface of discontinuity is possible
between A and B, for any given values of the temperature and
potentials, it will be impossible for that having the greater tension to
displace the other, at the temperature and with the potentials con-
sidered. Hence, when pc has the value determined by equation (571),
and consequently <rAo + o-BO *s one value of the tension for the surface
between A and B, it is impossible that the ordinary tension of the
surface crAB should be greater than this. If crAB = o-AC-f orBC, when
equation (571) is satisfied, we may presume that a thin film of the
phase C actually exists at the surface between A and B, and that a
variation of the phases such as would make p0 greater than the
second member of (571) cannot be brought about at that surface, as it
would be prevented by the formation of a larger mass of the phase C.
But if <rAB<<rAo+<rBc wnen equation (571) is satisfied, this equation
does not mark the limit of the stability of the surface between
A and B, for the temperature or potentials must receive a finite
change before the film of phase C, or (as we shall see in the
following paragraph) a lentiform mass of that phase, can be formed.
The work which must be expended in order to form on the surface
between indefinitely large masses of phases A and B a lentiform mass
of phase C in equilibrium, may evidently be represented by the
formula w „ „ „
— °"AC ^AC T O"BC ^BC —
B, (573)
where $AO, $BO denote the areas of the surfaces formed between A and
C, and B and C ; $AB the diminution of the area of the surface between
A and B; VG the volume formed of the phase C; and FA, FB the
diminution of the volumes of the phases A and B. Let us now
suppose crAc, OBC> O"AB> PA> PE t° remain constant and the external
boundary of the surface between A and B to remain fixed, while p0
increases and the surfaces of tension receive such alterations as are
necessary for equilibrium. It is not necessary that this should be
physically possible in the actual system ; we may suppose the changes
to take place, for the sake of argument, although involving changes
in the fundamental equations of the masses and surfaces considered.
Then, regarding W simply as an abbreviation for the second member
of the preceding equation, we have
d W= crAC dSAC + o-BO dSEG — o-AB dSAE
-pcdVc+pAdVA+pEdVB- Vcdpc. (574)
But the conditions of equilibrium require that
o-AC AC CTBC EO — crAB
0. (575)
264 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
Hence' dW=-V0dp0. (576)
Now it is evident that VG will diminish as p0 increases. Let us
integrate the last equation supposing p0 to increase from its original
value until Vc vanishes. This will give
W " - W = a negative quantity, (577)
where W and W" denote the initial and final values of W. But
W" = 0. Hence W is positive. But this is the value of W in the
original system containing the lentiform mass, and expresses the
work necessary to form the mass between the phases A and B. It
is therefore impossible that such a mass should form on a surface
between these phases. We must however observe the same limitation
as in the less general case already discussed, — that Pc—p±, PQ—PR
must not be so great that the dimensions of the lentiform mass are
of insensible magnitude. It may also be observed that the value of
these differences may be so small that there will not be room on the
surface between the masses of phases A and B for a mass of phase C
sufficiently large for equilibrium. In this case we may consider a
mass of phase C which is in equilibrium upon the surface between A
and B in virtue of a constraint applied to the line in which the three
surfaces of discontinuity intersect, which will not allow this line to
become longer, although not preventing it from becoming shorter.
We may prove that the value of W is positive by such an integration
as we have used before.
Substitution of Pressures for Potentials in Fundamental Equations
for Surfaces.
The fundamental equation of a surface which gives the value of
the tension in terms of the temperature and potentials seems best
adapted to the purposes of theoretical discussion, especially when the
number of components is large or undetermined. But the experi-
mental determination of the fundamental equations, or the application
of any result indicated by theory to actual cases, will be facilitated
by the use of other quantities in place of the potentials, which shall
be capable of more direct measurement, and of which the numerical
expression (when the necessary measurements have been made) shall
depend upon less complex considerations. The numerical value of a
potential depends not only upon the system of units employed, but
also upon the arbitrary constants involved in the definition of the
energy and entropy of the substance to which the potential relates,
or, it may be, of the elementary substances of which that substance
is formed. (See page 96.) This fact and the want of means of
direct measurement may give a certain vagueness to the idea of the
EQUILIBEIUM OF HETEROGENEOUS SUBSTANCES. 265
potentials, and render the equations which involve them less fitted to
give a clear idea of physical relations.
Now the fundamental equation of each of the homogeneous masses
which are separated by any surface of discontinuity affords a relation
between the pressure in that mass and the temperature and potentials.
We are therefore able to eliminate one or two potentials from the
fundamental equation of a surface by introducing the pressures in
the adjacent masses. Again, when one of these masses is a gas-
mixture which satisfies Dal ton's law as given on page 155, the
potential for each simple gas may be expressed in terms of the tem-
perature and the partial pressure belonging to that gas. By the
introduction of these partial pressures we may eliminate as many
potentials from the fundamental equation of the surface as there are
simple gases in the gas-mixture.
An equation obtained by such substitutions may be regarded as a
fundamental equation for the surface of discontinuity to which it
relates, for when the fundamental equations of the adjacent masses
are known, the equation in question is evidently equivalent to an
equation between the tension, temperature, and potentials, and we
must regard the knowledge of the properties of the adjacent masses
as an indispensable preliminary, or an essential part, of a complete
knowledge of any surface of discontinuity. It is evident, however,
that from these fundamental equations involving pressures instead
of potentials we cannot obtain by differentiation (without the use of
the fundamental equations of the homogeneous masses) precisely the
same relations as by the differentiation of the equations between the
tensions, temperatures, and potentials. It will be interesting to
inquire, at least in the more important cases, what relations may be
obtained by differentiation from the fundamental equations just
described alone.
If there is but one component, the fundamental equations of the
two homogeneous masses afford one relation more than is necessary
for the elimination of the potential. It may be convenient to regard
the tension as a function of the temperature and the difference of the
pressures. Now we have by (508) and (98)
do-— —
d(p' -p") = (
Hence we derive the equation
p"), (578)
which indicates the differential coefficients of o- with respect to t and
p'— p". For surfaces which may be regarded as nearly plane, it is
266 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
r
evident that —, T, represents the distance from the surface of
y-y
tension to a dividing surface located so as to make the superficial
density of the single component vanish (being positive, when the
latter surface is on the side specified by the double accents), and that
the coefficient of dt (without the negative sign) represents the super-
ficial density of entropy as determined by the latter dividing surface,
i.e., the quantity denoted by t]8(l) on page 235.
When there are two components, neither of which is confined to
the surface of discontinuity, we may regard the tension as a function
of the temperature and the pressures in the two homogeneous masses.
The values of the differential coefficients of the tension with respect
to these variables may be represented in a simple form if we choose
such substances for the components that in the particular state con-
sidered each mass shall consist of a single component. This will
always be possible when the composition of the two masses is not
identical, and will evidently not affect the values of the differential
coefficients. We then have
dp' = 77 v' dt + y dp, ,
where the marks , and u are used instead of the usual l and 2 to indi-
cate the identity of the component specified with the substance of
the homogeneous masses specified by ' and ". Eliminating dp, and
dfjia we obtain
/ T1 T \ T1 T
7 / J- i r -*- // ff\ 7j -*- / 7 / •*• - 7 » /K*7C\\
dcr = — { rjo ,t]y "i *7v ) dt — —, -, dp ", dp . (t> i v)
\ y y / y y
We may generally neglect the difference of pf and p", and write
'L/+Lt\dp. (580)
The equation thus modified is strictly to be regarded as the equation
r r
for a plane surface. It is evident that — > and -% represent the dis-
y y
tances from the surface of tension of the two surfaces of which one
r r
would make IV vanish, and the other r , that — ; • + — ", represents
y y
the distance between these two surfaces, or the diminution of volume
due to a unit of the surface of discontinuity, and that the coefficient
of dt (without the negative sign) represents the excess of entropy in
a system consisting of a unit of the surface of discontinuity with
a part of each of the adjacent masses above that which the same
matter would have if it existed in two homogeneous masses of the
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 267
same phases but without any surface of discontinuity. (A mass thus
existing without any surface of discontinuity must of course be
entirely surrounded by matter of the same phase.)*
The form in which the values of f-rrj and (-*-] are given in
\dt/p \dp/t
equation (580) is adapted to give a clear idea of the relations of
these quantities to the particular state of the system for which they
are to be determined, but not to show how they vary with the state
of the system. For this purpose it will be convenient to have the
values of these differential coefficients expressed with reference to
ordinary components. Let these be specified as usual by 1 and 2.
If we eliminate d^ and djuL2 from the equations
— da- = r]Bdt + 1\ d^ + F2 dfa,
dp = rjv'dt + y/d//! + y2'dyK2,
dp = ri^'dt + y/dy
we obtain
£ C
* If we set
and in like manner
r r
E — e ' t ' " *, " lt>\
s— es-— / *v --j/fv >
we may easily obtain, by means of equations (93) and (507),
Ea = tHs + <r-pV. (d)
Now equation (580) may be written
dff=-ILsdt+Vdp. (e)
Differentiating (d), and comparing the result with (e), we obtain
The quantities E8 and H8 might be called the superficial densities of energy and
entropy quite as properly as those which we denote by e8 and i)S. In fact, when the
composition of both of the homogeneous masses is invariable, the quantities E8 and Hg
are much more simple in their definition than es and r)S, and would probably be more
naturally suggested by the terms superficial density of energy and of entropy. It would
also be natural in this case to regard the quantities of the homogeneous masses as
determined by the total quantities of matter, and not by the surface of tension or any
other dividing surface. But such a nomenclature and method could not readily be
extended so as to treat cases of more than two components with entire generality.
In the treatment of surfaces of discontinuity in this paper, the definitions and
nomenclature which have been adopted will be strictly adhered to. The object of this
note is to suggest to the reader how a different method might be used in some cases
with advantage, and to show the precise relations between the quantities which are
used in this paper and others which might be confounded with them, and which may
be made more prominent when the subject is treated differently.
268 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES,
where
A=vi"y*-yi'y*"> (582)
T-l' T1
//S -L 1 -L 2
n\ y\ y* > (583)
ft // //
nv y\ 72
^=ri(y2//-y2/) + r2(y/-y1l. (584)
It will be observed that A vanishes when the composition of the two
homogeneous masses is identical, while B and C do not, in general,
and that the value of A is negative or positive according as the mass
specified by ' contains the component specified by x in a greater or
less proportion than the other mass. Hence, the values both of
(-T:} and of (-T-J become infinite when the difference in the com-
position of the masses vanishes, and change sign when the greater
proportion of a component passes from one mass to the other. This
might be inferred from the statements on page 99 respecting co-
existent phases which are identical in composition, from which it
appears that when two coexistent phases have nearly the same
composition, a small variation of the temperature or pressure of the
coexistent phases will cause a relatively very great variation in
the composition of the phases. The same relations are indicated by
the graphical method represented in figure 6 on page 125.
With regard to gas-mixtures which conform to Dalton's law, we
shall only consider the fundamental equation for plane surfaces, and
shall suppose that there is not more than one component in the liquid
which does not appear in the gas-mixture. We have already seen
that in limiting the fundamental equation to plane surfaces we can
get rid of one potential by choosing such a dividing surface that the
superficial density of one of the components vanishes. Let this be
done with respect to the component peculiar to the liquid, if such
there is; if there is no such component, let it be done with respect
to one of the gaseous components. Let the remaining potentials be
eliminated by means of the fundamental equations of the simple gases.
We may thus obtain an equation between the superficial tension, the
temperature, and the several pressures of the simple gases in the
gas-mixture or all but one of these pressures. Now, if we eliminate
dfjL2, dfjL3, etc. from the equations
dor = — t]S(i)dt — r2(1)cfyz2 — r3(1)cZ//3 — etc.,
! = J/V2<^ + 72<
etc.,
where the suffix 1 relates to the component of which the surface-
density has been made to vanish, and y2, y3, etc. denote the densities
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 269
of the gases specified in the gas-mixture, and p2, ps, etc.,
etc. the pressures and the densities of entropy due to these several
gases, we obtain
72
_ ?k> dp2 - ^ dp, - etc. (585)
72 73
This equation affords values of the differential coefficients of a- with
respect to t, p2, ps, etc., which may be set equal to those obtained
by differentiating the equation between these variables.
Thermal and Mechanical Relations pertaining to the Extension of a
Surface of Discontinuity.
The fundamental equation of a surface of discontinuity with one
or two component substances, besides its statical applications, is "of
use to determine the heat absorbed when the surface is extended
under certain conditions.
Let us first consider the case in which there is only a single
component substance. We may treat the surface as plane, and
place the dividing surface so that the surface density of the single
component vanishes. (See page 234.) If we suppose the area of the
surface to be increased by unity without change of temperature or
of the quantities of liquid and vapor, the entropy of the whole will
be increased by qsw. Therefore, if we denote by Q the quantity of
heat which must be added to satisfy the conditions, we shall have
Q = trjs(l)} ' (586)
and by (514),
«— — - (587)
It will be observed that the condition of constant quantities of liquid
and vapor as determined by the dividing surface which we have
adopted is equivalent to the condition that the total volume shall
remain constant.
Again, if the surface is extended without application of heat,
while the pressure in the liquid and vapor remains constant, the
temperature will evidently be maintained constant by condensation
of the vapor. If we denote by M the mass of vapor condensed per
unit of surface formed, and by 7/M' and 7/M" the entropies of the liquid
and vapor per unit of mass, the condition of no addition of heat
will require that
-V*) = *«• <588)
270 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
The increase of the volume of liquid will be
' (589)
and the diminution of the volume of vapor
a/ *;(1) — TV (590)
*%/ I 77 ff 1
Hence, for the work done (per unit of surface formed) by the
external bodies which maintain the pressure, we shall have
(591)
'/M — '/M vjr Y '
and, by (514) and (131),
-rrr_ d<T dt d(T _ d<T /KQO\
^ c££ c£p -*a_p dlogp'
The work expended directly in extending the film will of course
be equal to cr.
Let us now consider the case in which there are two component
substances, neither of which is confined to the surface. Since we
cannot make the superficial density of both these substances vanish
by any dividing surface, it will be best to regard the surface of
tension as the dividing surface. We may, however, simplify the
formula by choosing such substances for components that each homo-
geneous mass shall consist of a single component. Quantities relating
to these components will be distinguished as on page 266. If the
surface is extended until its area is increased by unity, while heat
is added at the surface so as to keep the temperature constant, and
the pressure of the homogeneous masses is also kept constant, the
phase of these masses will necessarily remain unchanged, but the
quantity of one will be diminished by F, , and that of the other by r,,.
r r
Their entropies will therefore be diminished by —,?]? and —jfrjy',
respectively. Hence, since the surface receives the increment of
entropy qa, the total quantity of entropy will be increased by
_r, ,_r, „
7/8 y' ^ 7" nv '
which by equation (580) is equal to
\dt/p'
Therefore, for the quantity of heat Q imparted to the surface, we
shall have
Q= _«(?£) =_(*!_). (593)
\dt/n \dLO£t/n
EQUILIBKIUM OF HETEROGENEOUS SUBSTANCES. 271
We must notice the difference between this formula and (587). In
(593) the quantity of heat Q is determined by the condition that the
temperature and pressures shall remain constant. In (587) these
conditions are equivalent and insufficient to determine the quantity
of heat. The additional condition by which Q is determined may be
most simply expressed by saying that the total volume must remain
constant. Again, the differential coefficient in (593) is defined by
considering p as constant ; in the differential coefficient in (587) p
cannot be considered as constant, and no condition is necessary
to give the expression a definite value. Yet, notwithstanding the
difference of the two cases, it is quite possible to give a single
demonstration which shall be applicable to both. This may be done
by considering a cycle of operations after the method employed by
Sir William Thomson, who first pointed out these relations.*
The diminution of volume (per unit of surface formed) will be
(594)
y y \p/t
and the work done (per unit of surface formed) by the external
bodies which maintain the pressure constant will be
da\ ( da- \
j-) = -(;JT- -)• (595)
dp/t \dlogp/t
Compare equation (592).
The values of Q and W may also be expressed in terms of quan-
tities relating to the ordinary components. By substitution in (593)
and (595) of the values of the differential coefficients which are given
by (581), we obtain
<2=-*f, w—*i* (596>
where A, B, and C represent the expressions indicated by (582)-(584).
It will be observed that the values of Q and W are in general infinite
for the surface of discontinuity between coexistent phases which
differ infinitesimally in composition, and change sign with the quantity
A. When the phases are absolutely identical in composition, it is not
in general possible to counteract the effect of extension of the surface
of discontinuity by any supply of heat. For the matter at the surface
will not in general have the same composition as the homogeneous
masses, and the matter required for the increased surface cannot be
obtained from these masses without altering their phase. The infinite
values of Q and W are explained by the fact that when the phases
are nearly identical in composition, the extension of the surface of
*See Proc. Hoy. Soc., vol. ix, p. 255 (June, 1858); or Phil. Mag., ser. 4, vol. xvii,
p. 61.
272 EQUILIBEIUM OF HETEROGENEOUS SUBSTANCES.
discontinuity is accompanied by the vaporization or condensation
of a very large mass, according as the liquid or the vapor is the richer
in that component which is necessary for the formation of the surface
of discontinuity.
If, instead of considering the amount of heat necessary to keep the
phases from altering while the surface of discontinuity is extended,
we consider the variation of temperature caused by the extension of
the surface while the pressure remains constant, it appears that this
variation of temperature changes sign with y\ y^—y^y^* but
vanishes with this quantity, i.e., vanishes when the composition of the
phases becomes the same. This may be inferred from the statements
on page 99, or from a consideration of the figure on page 125. When
the composition of the homogeneous masses is initially absolutely
identical, the effect on the temperature of a finite extension or
contraction of the surface of discontinuity will be the same, — either
of the two will lower or raise the temperature according as the
temperature is a maximum or minimum for constant pressure.
The effect of the extension of a surface of discontinuity which is
most easily verified by experiment is the effect upon the tension
before complete equilibrium has been reestablished throughout the
adjacent masses. A fresh surface between coexistent phases may be
regarded in this connection as an extreme case of a recently extended
surface. When sufficient time has elapsed after the extension of a
surface originally in equilibrium between coexistent phases, the
superficial tension will evidently have sensibly its original value,
unless there are substances at the surface which are either not found
at all in the adjacent masses, or are found only in quantities com-
parable to those in which they exist at the surface. But a surface
newly formed or extended may have a very different tension.
This will not be the case, however, when there is only a single
component substance, since all the processes necessary for equilibrium
are confined to a film of insensible thickness, and will require no
appreciable time for their completion.
When there are two components, neither of which is confined
to the surface of discontinuity, the reestablishment of equilibrium
after the extension of the surface does not necessitate any processes
reaching into the interior of the masses except the transmission of
heat between the surface of discontinuity and the interior of the
masses. It appears from equation (593) that if the tension of the
surface diminishes with a rise of temperature, heat must be supplied
to the surface to maintain the temperature uniform when the surface
is extended, i.e., the effect of extending the surface is to cool it ; but
if the tension of any surface increases with the temperature, the
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 273
effect of extending the surface will be to raise its temperature. In
either case, it will be observed, the immediate effect of extending the
surface is to increase its tension. A contraction of the surface will
of course have the opposite effect. But the time necessary for the
reestablishment of sensible thermal equilibrium after extension or
contraction of the surface must in most cases be very short.
In regard to the formation or extension of a surface between two
coexistent phases of more than two components, there are two
extreme cases which it is desirable to notice. When the superficial
density of each of the components is exceedingly small compared with
its density in either of the homogeneous masses, the matter (as well
as the heat) necessary for the formation or extension of the normal
surface can be taken from the immediate vicinity of the surface
without sensibly changing the properties of the masses from which it
is taken. But if any one of these superficial densities has a consider-
able value, while the density of the same component is very small in
each of the homogeneous masses, both absolutely and relatively to
the densities of the other components, the matter necessary for the
formation or extension of the normal surface must come from a
considerable distance. Especially if we consider that a small
difference of density of such a component in one of the homogeneous
masses will probably make a considerable difference in the value of
the corresponding potential {see eq. (217)}, and that a small difference
in the value of the potential will make a considerable difference in
the tension (see eq. (508)}, it will be evident that in this case a
considerable time will be necessary after the formation of a fresh
surface or the extension of an old one for the reestablishment of
the normal value of the superficial tension. In intermediate cases,
the reestablishment of the normal tension will take place with
different degrees of rapidity.
But whatever the number of component substances, provided that
it is greater than one, and whether the reestablishment of equilibrium
is slow or rapid, extension of the surface will generally produce
increase and contraction decrease of the tension. It would evidently
be inconsistent with stability that the opposite effects should be
produced. In general, therefore, a fresh surface between coexistent
phases has a greater tension than an old one.* By the use of fresh
surfaces, in experiments in capillarity, we may sometimes avoid the
effect of minute quantities of foreign substances, which may be
* When, however, homogeneous masses which have net coexistent phases are brought
into contact, the superficial tension may increase with the course of time. The
superficial tension of a drop of alcohol and water placed in a large room will increase as
the potential for alcohol is equalized throughout the room, and is diminished in the
vicinity of the surface of discontinuity.
G. I. S
274 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
present without our knowledge or desire, in the fluids which meet at
the surface investigated.
When the establishment of equilibrium is rapid, the variation of
the tension from its normal value will be manifested especially during
the extension or contraction of the surface, the phenomenon resembling
that of viscosity, except that the variations of tension arising from
variations in the densities at and about the surface will be the same
in all directions, while the variations of tension due to any property
of the surface really analogous to viscosity would be greatest in
the direction of the most rapid extension.
We may here notice the different action of traces in the homogeneous
masses of those substances which increase the tension and of those
which diminish it. When the volume-densities of a component are
very small, its surface-density may have a considerable positive value,
but can only have a very minute negative one.* For the value
when negative cannot exceed (numerically) the product of the
greater volume-density by the thickness of the non-homogeneous
film. Each of these quantities is exceedingly small. The surface-
density when positive is of the same order of magnitude as the
thickness of the non-homogeneous film, but is not necessarily small
compared with other surface-densities because the volume-densities
of the same substance in the adjacent masses are small. Now
the potential of a substance which forms a very small part of a
homogeneous mass certainly increases, and probably very rapidly, as
the proportion of that component is increased. {See (171) and (217).}
The pressure, temperature, and the other potentials, will not be
sensibly affected. {See (98).} But the effect on the tension of this
increase of the potential will be proportional to the surface-density,
and will be to diminish the tension when the surface-density is
positive. {See (508).} It is therefore quite possible that a very
small trace of a substance in the homogeneous masses should greatly
diminish the tension, but not possible that such a trace should
greatly increase it.t
*It is here supposed that we have chosen for components such substances as are
incapable of resolution into other components which are independently variable in the
homogeneous masses. In a mixture of alcohol and water, for example, the components
must be pure alcohol and pure water.
fFrom the experiments of M. E. Duclaux (Annales de Chimie et de Physique, ser. 4,
vol. xxi, p. 383), it appears that one per cent, of alcohol in water will diminish the
superficial tension to '933, the value for pure water being unity. The experiments do
not extend to pure alcohol, but the difference of the tensions for mixtures of alcohol
and water containing 10 and 20 per cent, water is comparatively small, the tensions
being -322 and '336 respectively.
According to the same authority (page 427 of the volume cited), one 3200th part of
Castile soap will reduce the superficial tension of water by one-fourth ; one 800th part
of soap by one-half. These determinations, as well as those relating to alcohol and
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 275
Impermeable Films.
We have so far supposed, in treating of surfaces of discontinuity,
that they afford no obstacle to the passage of any of the component
substances from either of the homogeneous masses to the other. The
case, however, must be considered, in which there is a film of matter
at the surface of discontinuity which is impermeable to some or all of
the components of the contiguous masses. Such may be the case,
for example, when a film of oil is spread on a surface of water, even
when the film is too thin to exhibit the properties of the oil in mass.
In such cases, if there is communication between the contiguous
masses through other parts of the system to which they belong, such
that the components in question can pass freely from one mass to the
other, the impossibility of a direct passage through the film may be
regarded as an immaterial circumstance, so far as states of equilibrium
are concerned, and our formulas will require no change. But when
there is no such indirect communication, the potential for any
component for which the film is impermeable may have entirely
different values on opposite sides of the film, and the case evidently
requires a modification of our usual method.
A single consideration will suggest the proper treatment of such
cases. If a certain component which is found on both sides of a film
cannot pass from either side to the other, the fact that the part of the
component which is on one side is the same kind of matter with the
part on the other side may be disregarded. All the general relations
must hold true, which would hold if they were really different
substances. We may therefore write fa for the potential of the
component on one side of the film, and /z2 for the potential of the
same substance (to be treated as if it were a different substance) on
the other side; m\ for the excess of the quantity of the substance
on the first side of the film above the quantity which would be on
that side of the dividing surface (whether this is determined by the
surface of tension or otherwise) if the density of the substance were
the same near the dividing surface as at a distance, and mf for a
similar quantity relating to the other side of the film and dividing
water, are made by the method of drops, the weight of the drops of different liquids
(from the same pipette) being regarded as proportional to their superficial tensions.
M. Athanase Dupr4 has determined the superficial tensions of solutions of soap by
different methods. A statical method gives for one part of common soap in 5000 of
water a superficial tension about one-half as great as for pure water, but if the tension
be measured on a jet close to the orifice, the value (for the same solution) is sensibly
identical with that of pure water. He explains these different values of the superficial
tension of the same solution as well as the great effect on the superficial tension
which a very small quantity of soap or other trifling impurity may produce, by the
tendency of the soap or other substance to form a film on the surface of the liquid.
(See Annales de Chimie et de Physique, ser. 4, vol. vii, p. 409, and vol. ix, p. 379.)
276 EQUILIBKIUM OF HETEROGENEOUS SUBSTANCES.
surface. On the same principle, we may use I\ and T2 to denote the
values of mf and m| per unit of surface, and m/, m2", y/, y2" ^°
denote the quantities of the substance and its densities in the two
homogeneous masses.
With such a notation, which may be extended to cases in which
the film is impermeable to any number of components, the equations
relating to the surface and the contiguous masses will evidently have
the same form as if the substances specified by the different suffixes
were all really different. The superficial tension will be a function
of fa and fj.2 , with the temperature and the potentials for the
other components, and — 1\ , — F2 will be equal to its differential
coefficients with respect to fa and //2. In a word, all the general
relations which have been demonstrated may be applied to this
case, if we remember always to treat the component as a different
substance according as it is found on one side or the other of the
impermeable film.
When there is free passage for the component specified by the
suffixes l and 2 through other parts of the system (or through any
flaws in the film), we shall have in case of equilibrium fa = fa. ^
we wish to obtain the fundamental equation for the surface when
satisfying this condition, without reference to other possible states
of the surface, we may set a single symbol for fa and fa in the
more general form of the fundamental equation. Cases may occur
of an impermeability which is not absolute, but which renders the
transmission of some of the components exceedingly slow. In such
cases, it may be necessary to distinguish at least two Different
fundamental equations, one relating to a state of approximate
equilibrium which may be quickly established, and another relating
to the ultimate state of complete equilibrium. The latter may be
derived from the former by such substitutions as that just indicated.
The Conditions of Internal Equilibrium for a System of Hetero-
geneous Fluid Masses without neglect of the Influence of the
Surfaces of Discontinuity or of Gravity.
Let us now seek the complete value of the variation of the energy
of a system of heterogeneous fluid masses, in which the influence of
gravity and of the surfaces of discontinuity shall be included, and
deduce from it the conditions of internal equilibrium for such a
system. In accordance with the method which has been developed,
the intrinsic energy (i.e. the part of the energy which is independent
of gravity), the entropy, and the quantities of the several components
must each be divided into two parts, one of which we regard as
belonging to the surfaces which divide approximately homogeneous
EQUILIBEIUM OF HETEROGENEOUS SUBSTANCES. 277
masses, and the other as belonging to these masses. The elements
of intrinsic energy, entropy, etc., relating to an element of surface
Ds will be denoted by De8, Drj9, Dm\ , Draf , etc., and those relating
to an element of volume Dv, by Dev, Dif, Dm\, Dnil, etc. We
shall also use Dm8 or F Ds and Dmv or y Dv to denote the total
quantities of matter relating to the elements Ds and Dv respectively.
That is,
Dm9 = T Zte = Dm* + Dm9 + etc., (597)
Dinv = yDv = Dm\ + Dm\ + etc. (598)
The part of the energy which is due to gravity must also be divided
into two parts, one of which relates to the elements Dm9, and the
other to the elements Dmv. The complete value of the variation of
the energy of the system will be represented by the expression
SfDey + 8/De9 + 8 fgz Dm? + 8 fgz Dm9, (599)
in which g denotes the force of gravity, and z the height of the
element above a fixed horizontal plane.
It will be convenient to limit ourselves at first to the consideration
of reversible variations. This will exclude the formation of new
masses or surfaces. We may therefore regard any infinitesimal
variation in the state of the system as consisting of infinitesimal
variations of the quantities relating to its several elements, and
bring the sign of variation in the preceding formula after the sign
of integration. If we then substitute for 8Dey, <5De8, 8Dmy, 8 Dm9,
the values given by equations (13), (497), (597), (598), we shall have
for the condition of equilibrium with respect to reversible variations
of the internal state of the system
ft 8Dr]v - fp SDv+ffr SDrnl+fjuL2 8Dm1+etc.
+ft 8 Drj9 + fa- 8 Ds + /X 8 Dm9 + />2 8 Dm9 + etc.
+fg 8z Dmv +fgz 8 Dm\ + fgz 8 Dm\ + etc.
+fg 8z Dm9 +fgz S Dm\ + fgz 8 Dm\ + etc. = 0. (600)
Since equation (497) relates to surfaces of discontinuity which are
initially in equilibrium, it might seem that this condition, although
always necessary for equilibrium, may not always be sufficient. It
is evident, however, from the form of the condition, that it includes
the particular conditions of equilibrium relating to every possible
deformation of the system, or reversible variation in the distribution
of entropy or of the several components. It therefore includes
all the relations between the different parts of the system which
are necessary for equilibrium, so far as reversible variations are
concerned. (The necessary relations between the various quantities
relating to each element of the masses and surfaces are expressed
278
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
by the fundamental equation of the mass or surface concerned, or may
be immediately derived from it. See pp. 85-89 and 229-231.)
The variations in (600) are subject to the conditions which arise
from the nature of the system and from the supposition that the
changes in the system are not such as to affect external bodies. This
supposition is necessary, unless we are to consider the variations in
the state of the external bodies, and is evidently allowable in seeking
the conditions of equilibrium which relate to the interior of the
system.* But before we consider the equations of condition in
detail, we may divide the condition of equilibrium (600) into the
three conditions
(601)
(602)
-fp SD
v
fo-SDs + fgSz Dmv +fgSz Dm8 = 0,
1+fgztDml
+ fgz SDrnl + fgz 8 Dm8
+ etc. = 0.
(603)
For the variations which occur in any one of the three are evidently
independent of those which occur in the other two, and the equations
of condition will relate to one or another of these conditions
separately.
The variations in condition (601) are subject to the condition that
the entropy of the whole system shall remain constant. This may be
expressed by the equation
fSDr}v+fSDr)8 = 0. (604)
To satisfy the condition thus limited it is necessary and sufficient that
t = const. (605)
throughout the whole system, which is the condition of thermal
equilibrium.
The conditions of mechanical equilibrium, or those that relate to
the possible deformation of the system, are contained in (602), which
may also be written
zDs = Q. (606;
*We have sometimes given a physical expression to a supposition of this kind,
problems in which the peculiar condition of matter in the vicinity of surfaces
discontinuity was to be neglected, by regarding the system as surrounded by a rigid and
impermeable envelop. But the more exact treatment which we are now to give the
problem of equilibrium would require us to take account of the influence of the envelop
on the immediately adjacent matter. Since this involves the consideration of surfaces
of discontinuity between solids and fluids, and we wish to limit ourselves at present
to the consideration of the equilibrium of fluid masses, we shall give up the conception
of an impermeable envelop, and regard the system as bounded simply by an imaginary
surface, which is not a surface of discontinuity. The variations of the system must be
such as do not deform the surface, nor affect the matter external to it.
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 279
It will be observed that this condition has the same form as if
the different fluids were separated by heavy and elastic membranes
without rigidity and having at every point a tension uniform in
all directions in the plane of the surface. The variations in this
formula, beside their necessary geometrical relations, are subject to
the conditions that the external surface of the system, and the lines
in which the surfaces of discontinuity meet it, are fixed. The formula
may be reduced by any of the usual methods, so as to give the
particular conditions of mechanical equilibrium. Perhaps the following
method will lead as directly as any to the desired result.
It will be observed the quantities affected by S in (606) relate
exclusively to the position and size of the elements of volume and
surface into which the system is divided, and that the variations Sp
and So- do not enter into the formula either explicitly or implicitly.
The equations of condition which concern this formula also relate
exclusively to the variations of the system of geometrical elements,
and do not contain either Sp or Sar. Hence, in determining whether
the first member of the formula has the value zero for every possible
variation of the system of geometrical elements, we may assign to
Sp and So- any values whatever which may simplify the solution of
the problem, without inquiring whether such values are physically
possible.
Now when the system is in its initial state, the pressure p, in each
of the parts into which the system is divided by the surfaces of
tension, is a function of the co-ordinates which determine the position
of the element Dv, to which the pressure relates. In the varied state
of the system, the element Dv will in general have a different position.
Let the variation Sp be determined solely by the change in position
of the element Dv. This may be expressed by the equation
(607)
in which -£-, -£-, -f- are determined by the function mentioned,
dx ay dz
and Sx, Sy, Sz by the variation of the position of the element Dv.
Again, in the initial state of the system the tension a; in each of
the different surfaces of discontinuity, is a function of two co-ordinates
o)l, ft>2, which determine the position of the element Ds. In the varied
state of the system, this element will in general have a different
position. The change of position may be resolved into a component
lying in the surface and another normal to it. Let the variation So-
be determined solely by the first of these components of the motion of
Ds. This may be expressed by the equation
*-**+** (608)
280 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
in which -* — , -j — are determined by the function mentioned, and
&*>!, So)2, by the component of the motion of Ds which lies in the
plane of the surface.
With this understanding, which is also to apply to Sp and So-
when contained implicitly in any expression, we shall proceed to the
reduction of the condition (606).
With respect to any one of the volumes into which the system is
divided by the surfaces of discontinuity, we may write
fpSDv = Sfp Dv-fSp Dv.
But it is evident that
SfpDv=fpSNDs,
where the second integral relates to the surfaces of discontinuity
bounding the volume considered, and SN denotes the normal
component of the motion of an element of the surface, measured
outward. Hence,
fpSDv=fpSNDs -fSp Dv.
Since this equation is true of each separate volume into which the
system is divided, we may write for the whole system
fpS Dv=f(p'-p")SN Ds-fSp Dv, (609)
where p' and p" denote the pressures on opposite sides of the element
Ds, and SN is measured toward the side specified by double accents.
Again, for each of the surfaces of discontinuity, taken separately,
f<rSDs = 8 fa- Ds - fSa- Ds,
and
where cx and cz denote the principal curvatures of the surface
(positive, when the centers are on the side opposite to that toward
which SN is measured), Dl an element of the perimeter of the surface,
and ST the component of the motion of this element which lies in the
plane of the surface and is perpendicular to the perimeter (positive,
when it extends the surface). Hence we have for the whole system
fa- SDs =f<r(cl + c2) 8NDa+f2(<r ST) Dl-fS<r Ds, (610)
where the integration of the elements Dl extends to all the lines in
which the surfaces of discontinuity meet, and the symbol 2 denotes
a summation with respect to the several surfaces which meet in such
a line.
By equations (609) and (610), the general condition of mechanical
equilibrium is reduced to the form
- / (Pf -P") SN Ds +fSp Dv +/<r (cx + c2) 8N Ds
+/2 (o- ST) Dl -fSa- Ds +fgy Sz Dv +fgT Sz Ds = 0.
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 281
Arranging and combining terms, we have
f(gy to + Sp) Dv +f[(p"-p') SN+ <T(CI + c2) SN+gT Sz - fo] Da
+/2(<r<$T)DJ = 0. (611)
To satisfy this condition, it is evidently necessary that the coefficients
of Dv, Ds, and Dl shall vanish throughout the system.
In order that the coefficient of Dv shall vanish, it is necessary and
sufficient that in each of the masses into which the system is divided
by the surfaces of tension, p shall be a function of z alone, such that
In order that the coefficient of Ds shall vanish in all cases, it is
necessary and sufficient that it shall vanish for normal and for
tangential movements of the surface. For normal movements we
may write
&r = 0 and Sz
where 0 denotes the angle which the normal makes with a vertical
line. The first condition therefore gives the equation
(613)
which must hold true at every point in every surface of discontinuity.
The condition with respect to tangential movements shows that in
each surface of tension a- is a function of z alone, such that
In order that the coefficient of Dl in (611) shall vanish, we must
have, for every point in every line in which surfaces of discontinuity
meet, and for any infinitesimal displacement of the line,
2(<r<JT) = 0. (615)
This condition evidently expresses the same relations between the
tensions of the surfaces meeting in the line and the directions of
perpendiculars to the line drawn in the planes of the various surfaces,
which hold for the magnitudes and directions of forces in equilibrium
in a plane.
In condition (603), the variations which relate to any component are
to be regarded as having the value zero in any part of the system in
which that substance is not an actual component.* The same is true
*The term actual component has been defined for homogeneous masses on page 64,
and the definition may be extended to surfaces of discontinuity. It will be observed
that if a substance is an actual component of either of the masses separated by a surface
of discontinuity, it must be regarded as an actual component for that surface, as well as
when it occurs at the surface but not in either of the contiguous masses.
282 EQUILIBEIUM OF HETEROGENEOUS SUBSTANCES.
with respect to^the^equations of condition, which are of the form
(616)
etc.
(It is here supposed that the various components are independent, i.e.,
that none can be formed out of others, and that the parts of the
system in which any component actually occurs are not entirely
separated by parts in which it does not occur.) To satisfy the
condition (603), subject to these equations of condition, it is necessary
and sufficient that the conditions
*-Mv\
(617)
(Ml ,M2 , etc. denoting constants,) shall each hold true in those parts
of the system in which the substance specified is an actual component.
We may here add the condition of equilibrium relative to the possible
absorption of any substance (to be specified by the suffix a) by parts
of the system of which it is not an actual component, viz., that the
expression ^a-\-gz must not have a less value in such parts of the
system than in a contiguous part in which the substance is an actual
component.
From equation (613) with (605) and (617) we may easily obtain
the differential equation of a surface of tension (in the geometrical
sense of the term), when pr, p"y and <j are known in terms of the
temperature and potentials. For c-t + c2 and 0 may be expressed in
terms of the first and second differential coefficients of z with respect
to the horizontal co-ordinates, and p't p", or, and T in terms of the
temperature and potentials. But the temperature is constant, and for
each of the potentials we may substitute — gz increased by a constant.
We thus obtain an equation in which the only variables are z and its
first and second differential coefficients with respect to the horizontal
co-ordinates. But it will rarely be necessary to use so exact a method.
Within moderate differences of level, we may regard y ', y", and or as
constant. We may then integrate the equation {derived from (612)}
d(p'-p")=g(7"-y)dz,
which will give
p'-p"=9(y"-y)z, (618)
where z is to be measured from the horizontal plane for which p'=p".
Substituting this value in (613), and neglecting the term containing
T, we have
(619)
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 283
where the coefficient of z is to be regarded as constant. Now the
value of z cannot be very large, in any surface of sensible dimensions,
unless y" — y is very small. We may therefore consider this equation
as practically exact, unless the densities of the contiguous masses are
very nearly equal. If we substitute for the sum of the curvatures
its value in terms of the differential coefficients of z with respect to
the horizontal rectangular co-ordinates, x and y, we have
/ dz*\d*z ^dz dz d2z / dz^\d2z
dy2Jdx2 dxdydxdy \ dx2/dy2 <y(y"_y')
~ -*• (620)
With regard to the sign of the root in the denominator of the fraction,
it is to be observed that, if we always take the positive value of
the root, the value of the whole fraction will be positive or negative
according as the greater concavity is turned upward or downward.
But we wish the value of the fraction to be positive when the greater
concavity is turned toward the mass specified by a single accent.
We should therefore take the positive or negative value of the root
according as this mass is above or below the surface.
The particular conditions of equilibrium which are given in the
last paragraph but one may be regarded in general as the conditions
of chemical equilibrium between the different parts of the system,
since they relate to the separate components.* But such a designation
is not entirely appropriate unless the number of components is greater
than one. In no case are the conditions of mechanical equilibrium
entirely independent of those which relate to temperature and the
potentials. For the conditions (612) and (614) may be regarded as
consequences of (605) and (617) in virtue of the necessary relations
(98) and (508). t
The mechanical conditions of equilibrium, however, have an especial
importance, since we may always regard them as satisfied in any
liquid (and not decidedly viscous) mass in which no sensible motions
are observable. In such a mass, when isolated, the attainment of
mechanical equilibrium will take place very soon; thermal and chemical
equilibrium will follow more slowly. The thermal equilibrium will
generally require less time for its approximate attainment than the
chemical; but the processes by which the latter is produced will
generally cause certain inequalities of temperature until a state of
complete equilibrium is reached.
* Concerning another kind of conditions of chemical equilibrium, which relate to the
molecular arrangement of the components, and not to their sensible distribution in
space, see pages 138-144.
t Compare page 146, where a similar problem is treated without regard to the influence
of the surfaces of discontinuity.
284 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
When a surface of discontinuity has more components than one
which do not occur in the contiguous masses, the adjustment of the
potentials for these components in accordance with equations (617)
may take place very slowly, or not at all, for want of sufficient
mobility in the components of the surface. But when this surface
has only one component which does not occur in the contiguous
masses, and the temperature and potentials in these masses satisfy
the conditions of equilibrium, the potential for the component peculiar
to the surface will very quickly conform to the law expressed in (617),
since this is a necessary consequence of the condition of mechanical
equilibrium (614) in connection with the conditions relating to tem-
perature and the potentials which we have supposed to be satisfied.
The necessary distribution of the substance peculiar to the surface
will be brought about by expansions and contractions of the surface.
If the surface meets a third mass containing this component and no
other which is foreign to the masses divided by the surface, the
potential for this component in the surface will of course be deter-
mined by that in the mass which it meets.
The particular conditions of mechanical equilibrium (612)-(615),
which may be regarded as expressing the relations which must subsist
between contiguous portions of a fluid system in a state of mechanical
equilibrium, are serviceable in determining whether a given system
is or is not in such a state. But the mechanical theorems which
relate to finite parts of the system, although they may be deduced
from these conditions by integration, may generally be more easily
obtained by a suitable application of the general condition of
mechanical equilibrium (606), or by the application of ordinary
mechanical principles to the system regarded as subject to the forces
indicated by this equation.
It will be observed that the conditions of equilibrium relating to
temperature and the potentials are not affected by the surfaces of
discontinuity. {Compare (228) and (234). }* Since a phase cannot
vary continuously without variations of the temperature or the
potentials, it follows from these conditions that the phase at any
point in a fluid system which has the same independently variable
components throughout, and is in equilibrium under the influence of
gravity, must be one of a certain number of phases which are
completely determined by the phase at any given point and the
difference of level of the two points considered. If the phases
* If the fluid system is divided into separate masses by solid diaphragms which are
permeable to all the components of the fluids independently, the conditions of equi-
librium of the fluids relating to temperature and the potentials will not be affected.
(Compare page 84.) The propositions which follow in the above paragraph may be
extended to this case.
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 285
throughout the fluid system satisfy the general condition of practical
stability for phases existing in large masses (viz., that the pressure
shall be the least consistent with the temperature and potentials),
they will be entirely determined by the phase at any given point and
the differences of level. (Compare page 149, where the subject is
treated without regard to the influence of the surfaces of discon-
tinuity.)
Conditions of equilibrium relating to irreversible changes. — The
conditions of equilibrium relating to the absorption, by any part of
the system, of substances which are not actual components of that part
have been given on page 282. Those relating to the formation of
new masses and surfaces are included in the conditions of stability
relating to such changes, and are not always distinguishable from
them. They are evidently independent of the action of gravity. We
have already discussed the conditions of stability with respect to
the formation of new fluid masses within a homogeneous fluid and at
the surface when two such masses meet (see pages 252-264), as well
as the condition relating to the possibility of a change in the nature
of a surface of discontinuity. (See pages 237-240, where the surface
considered is plane, but the result may easily be extended to curved
surfaces.) We shall hereafter consider, in some of the more import-
ant cases, the conditions of stability with respect to the formation
of new masses and surfaces which are peculiar to lines in which
several surfaces of discontinuity meet, and points in which several
such lines meet.
Conditions of stability relating to the whole system. — Besides the
conditions of stability relating to very small parts of a system,
which are substantially independent of the action of gravity, and
are discussed elsewhere, there are other conditions, which relate to
the whole system or to considerable parts of it. To determine the
question of the stability of a given fluid system under the influence
of gravity, when all the conditions of equilibrium are satisfied as
well as those conditions of stability which relate to small parts of
the system taken separately, we may use the method described on
page 249, the demonstration of which (pages 247, 248) will not
require any essential modification on account of gravity.
When the variations of temperature and of the quantities Mlt M2,
etc. {see (617)} involved in the changes considered are so small that
they may be neglected, the condition of stability takes a very simple
form, as we have already seen to be the case with respect to a
system uninfluenced by gravity. (See page 251.)
We have to consider a varied state of the system in which the
total entropy and the total quantities of the various components are
unchanged, and all variations vanish at the exterior of the system, —
286 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
in which, moreover, the conditions of equilibrium relating to tem-
perature and the potentials are satisfied, and the relations expressed
by the fundamental equations of the masses and surfaces are to be
regarded as satisfied, although the state of the system is not one
of complete equilibrium. Let us imagine the state of the system
to vary continuously in the course of time in accordance with these
conditions and use the symbol d to denote the simultaneous changes
which take place at any instant. If we denote the total energy of
the system by E, the value of dE may be expanded like that
of SE in (599) and (600), and then reduced (since the values of
^> luii+9z> Pz+yZ) etc., are uniform throughout the system, and the
total entropy and total quantities of the several components are
constant) to the form
dE = -fp dDv +fg dz Dmv +fo- dDs +fg dz Dm*
= -fp dDv+fg y dz Dv+fo- dDs+fg T dz Ds, (621)
where the integrations relate to the elements expressed by the
symbol D. The value of p at any point in any of the various
masses, and that of a- at any point in any of the various surfaces
of discontinuity are entirely determined by the temperature and
potentials at the point considered. If the variations of t and Mv
M2 , etc. are to be neglected, the variations of p and or will be
determined solely by the change in position of the point considered.
Therefore, by (612) and (614),
dp=—gydz, dar=gTdz',
and ,- •.
dE = -fp dDv -fdp Dv +f<r dDs +fd<r Ds
= - dfp Dv + dfa- Ds. (622)
If we now integrate with respect to d, commencing at the given state
of the system, we obtain
AE = - &fp Dv + A/<r Ds, (623)
where A denotes the value of a quantity in a varied state of the
system diminished by its value in the given state. This is true for
finite variations, and is therefore true for infinitesimal variations
without neglect of the infinitesimals of the higher orders. The con-
dition of stability is therefore that
A/p Dv - A/o- Ds < 0, (624)
or that the quantity
fpDv-fcrDs (625)
has a maximum value, the values of p and cr, for each different mass
or surface, being regarded as determined functions of z. (In ordinary
cases cr may be regarded as constant in each surface of discontinuity,
and p as a linear function of z in each different mass.) It may easily
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
287
be shown (compare page 252) that this condition is always sufficient
for stability with reference to motion of surfaces of discontinuity,
even when the variations of t, M1> M2, etc. cannot be neglected in the
determination of the necessary condition of stability with respect to
such changes.
On the Possibility of the Formation of a New Surface of Discon-
tinuity where several Surfaces of Discontinuity meet.
When more than three surfaces of discontinuity between homo-
geneous masses meet along a line, we may conceive of a new surface
being formed between any two of the masses which do not meet in a
surface in the original state of the system. The condition of stability
with respect to the formation of such a surface may be easily obtained
by the consideration of the limit between stability and instability, as
exemplified by a system which is in equilibrium when a very small
surface of the kind is formed.
To fix our ideas, let us suppose that there are four homogeneous
masses A, B, C, and D, which meet one another in four surfaces,
which we may call A-B, B-C, C-D, and D-A, these surfaces all meeting
along a line L. This is indicated in figure 11 by a section of the
Fig. 11.
Fig. 12.
Fig. 13.
surfaces cutting the line L at right angles at a point 0. In an
infinitesimal variation of the state of the system, we may conceive of
a small surface being formed between A and C (to be called A-C),
so that the section of the surfaces of discontinuity by the same plane
takes the form indicated in figure 12. Let us suppose that the
condition of equilibrium (615) is satisfied both for the line L in which
the surfaces of discontinuity meet in the original state of the system,
and for the two such lines (which we may call L' and L") in the
varied state of the system, at least at the points 0' and O" where
they are cut by the plane of section. We may therefore form a
quadrilateral of which the sides a/3, /3y, yS, Sa are equal in numerical
value to the tensions of the several surfaces A-B, B-C, C-D, D-A,
and are parallel to the normals to these surfaces at the point O in
the original state of the system. In like manner, for the varied state
288 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
of the system we can construct two triangles having similar relations
to the surfaces of discontinuity meeting at O' and O". But the
directions of the normals to the surfaces A-B and B-C at O' and to
C-D and D-A at 0" in the varied state of the system differ infinitely
little from the directions of the corresponding normals at O in the
initial state. We may therefore regard a/3, /3y as two sides of the
triangle representing the surfaces meeting at 0', and yS, Sa as two
sides of the triangle representing the surfaces meeting at O". There-
fore, if we join ay, this line will represent the direction of the normal
to the surface A-C, and the value of its tension. If the tension of a
surface between such masses as A and C had been greater than that
represented by ay, it is evident that the initial state of the system
of surfaces (represented in figure 11) would have been stable with
respect to the possible formation of any such surface. If the tension
had been less, the state of the system would have been at least
practically unstable. To determine whether it is unstable in the
strict sense of the term, or whether or not it is properly to be
regarded as in equilibrium, would require a more refined analysis
than we have used.*
The result which we have obtained may be generalized as follows.
When more than three surfaces of discontinuity in a fluid system
meet in equilibrium along a line, with respect to the surfaces and
masses immediately adjacent to any point of this line, we may form
a polygon of which the angular points shall correspond in order to
the different masses separated by the surfaces of discontinuity, and
* We may here remark that a nearer approximation in the theory of equilibrium and
stability might be attained by taking special account, in our general equations, of the
lines in which surfaces of discontinuity meet. These lines might be treated in a
manner entirely analogous to that in which we have treated surfaces of discontinuity.
We might recognize linear densities of energy, of entropy, and of the several sub-
stances which occur about the line, also a certain linear tension. With respect to
these quantities and the temperature and potentials, relations would hold analogous to
those which have been demonstrated for surfaces of discontinuity. (See pp. 229-231.)
If the sum of the tensions of the lines L' and L", mentioned above, is greater than the
tension of the line L, this line will be in strictness stable (although practically unstable)
with respect to the formation of a surface between A and C, when the tension of such
a surface is a little less than that represented by the diagonal ay.
The different use of the term practically unstable in different parts of this paper need
not create confusion, since the general meaning of the term is in all cases the same.
A system is called practically unstable when a very small (not necessarily indefinitely
small) disturbance or variation in its condition will produce a considerable change.
In the former part of this paper, in which the influence of surfaces of discontinuity
was neglected, a system was regarded as practically unstable when such a result
would be produced by a disturbance of the same order of magnitude as the quantities
relating to surfaces of discontinuity which were neglected. But where surfaces of
discontinuity are considered, a system is not regarded as practically unstable, unless
the disturbance which will produce such a result is very small compared with the
quantities relating to surfaces of discontinuity of any appreciable magnitude.
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 289
the sides to these surfaces, each side being perpendicular to the
corresponding surface, and equal to its tension. With respect to
the formation of new surfaces of discontinuity in the vicinity of the
point especially considered, the system is stable, if every diagonal
of the polygon is less, and practically unstable, if any diagonal is
greater, than the tension which would belong to the surface of dis-
continuity between the corresponding masses. In the limiting case,
when the diagonal is exactly equal to the tension of the corresponding
surface, the system may often be determined to be unstable by the
application of the principle enunciated to an adjacent point of the
line in which the surfaces of discontinuity meet. But when, in
the polygons constructed for all points of the line, no diagonal is in
any case greater than the tension of the corresponding surface, but
a certain diagonal is equal to the tension in the polygons constructed
for a finite portion of the line, farther investigations are necessary
to determine the stability of the system. For this purpose, the
method described on page 249 is evidently applicable.
A similar proposition may be enunciated in many cases with
respect to a point about which the angular space is divided into
solid angles by surfaces of discontinuity. If these surfaces are in
equilibrium, we can always form a closed solid figure without re-
entrant angles of which the angular points shall correspond to the
several masses, the edges to the surfaces of discontinuity, and the
sides to the lines in which these edges meet, the edges being per-
pendicular to the corresponding surfaces, and equal to their tensions,
and the sides being perpendicular to the corresponding lines. Now
if the solid angles in the physical system are such as may be sub-
tended by the sides and bases of a triangular prism enclosing the
vertical point, or can be derived from such by deformation, the
iigure representing the tensions will have the form of two triangular
pyramids on opposite sides of the same base, and the system will
be stable or practically unstable with respect to the formation of
a surface between the masses which only meet in a point, according
as the tension of a surface between such masses is greater or less
than the diagonal joining the corresponding angular points of the
solid representing the tensions. This will easily appear on consider-
ation of the case in which a very small surface between the masses
would be in equilibrium.
The Conditions of Stability for Fluids relating to ike Formation
of a New Phase at a Line in which Three Surfaces of Dis-
continuity meet.
With regard to the formation of new phases there are particular
conditions of stability which relate to lines in which several surfaces
G.I. T
290
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
of discontinuity meet. We may limit ourselves to the case in which
there are three such surfaces, this being the only one of frequent
occurrence, and may treat them as meeting in a straight line. It
will be convenient to commence by considering the equilibrium of a
system in which such a line is replaced by a filament of a different
phase.
Let us suppose that three homogeneous fluid masses, A, B, and C
are separated by cylindrical (or plane) surfaces, A-B, B-C, C-A, which
at first meet in a straight line, each of the surface-tensions <rAB, erBC, orCA
being less than the sum of the other two. Let us suppose that the-
system is then modified by the introduction of a fourth fluid mass D,
which is placed between A, B, and C, and is separated from them by
cylindrical surfaces D-A, D-B, D-C meeting A-B, B-C, and C-A in
straight lines. The general form of the surfaces is shown by figure 14^
in which the full lines represent a section perpendicular to all the
surfaces. The system thus modified is to be in equilibrium, as well
as the original system, the position of the surfaces A-B, B-C, C-A
being unchanged. That the last condition is consistent with equili-
brium will appear from the following mechanical considerations.
FIG. 14.
Fm. 15.
FIG. 16.
Let V-Q denote the volume of the mass D per unit of length or the area
of the curvilinear triangle abc. Equilibrium is evidently possible for
any values of the surface tensions (if only arAE, <TBC> O"CA satisfy the con-
dition mentioned above, and the tensions of the three surfaces meet-
ing at each of the edges of D satisfy a similar condition) with any
value (not too large) of %>, if the edges of D are constrained to remain
in the original surfaces A-B, B-C, and C-A, or these surfaces extended,
if necessary, without change of curvature. (In certain cases one of
the surfaces DA, D-B, D-C may disappear and D will be bounded
by only two cylindrical surfaces.) We may therefore regard the
system as maintained in equilibrium by forces applied to the edges
of D and acting at right angles to A-B, B-C, C-A. The same forces
would keep the system in equilibrium if D were rigid. They must
therefore have a zero resultant, since the nature of the mass D is im-
material when it is rigid, and no forces external to the system would
be required to keep a corresponding part of the original system in
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 291
equilibrium. But it is evident from the points of application and
directions of these forces that they cannot have a zero resultant unless
each force is zero. We may therefore introduce a fourth mass D
without disturbing the parts which remain of the surfaces A-B, B-C,
C-D.
It will be observed that all the angles at a, b, c, and d in figure 14
are entirely determined by the six surface-tensions <TAB> O"BO» O"CA> O"DA>
<TDB> O"DC- (See (615).) The angles may be derived from the tensions
by the following construction, which will also indicate some important
properties. If we form a triangle afiy (figure 15 or 16) having sides
equal to O-AB> O"BO> <*"OA> ^ne angles of the triangle will be supplements
of the angles at d. To fix our ideas, we may suppose the sides of the
triangle to be perpendicular to the surfaces at d. Upon /3y we may
then construct (as in figure 16) a triangle f3y$ having sides equal
to (7Bc> 0"DC> 0"DB» upon ya a triangle yaS" having sides equal to
0"CA> O"DA> O"DC> and upon a/3 a triangle a/3S'" having sides equal to
O"AB> O"DB> O"DA- These triangles are to be on the same sides of the lines
/Sy, ya, aft, respectively, as the triangle a/3y. The angles of these
triangles will be supplements of the angles of the surfaces of discon-
tinuity at a, 6, and c. Thus fiyft = dab, and ayS" = dba. Now if $
and 8' fall together in a single point S within the triangle a/3y, ft"
will fall in the same point, as in figure 15. In this case we shall have
/8y<S -f- ay<$ = ay ft, and the three angles of the curvilinear triangle adb
will be together equal to two right angles. The same will be true of
the three angles of each of the triangles bdc, cda, and hence of the
three angles of the triangle abc. But if S', S", 8" do not fall together
in the same point within the triangle a/3y, it is either possible to
bring these points to coincide within the triangle by increasing some
or all of the tensions o-DA, o-DB> 0"DC> or t° effect the same result by
diminishing some or all of these tensions. (This will easily appear
when one of the points &, <T, 8" falls within the triangle, if we let the
two tensions which determine this point remain constant, and the
third tension vary. When all the points S', 8", S"' fall without
the triangle a/3y, we may suppose the greatest of the tensions
O"DA> o"DB> 0"Dc — tne fcwo greatest, when these are equal, and all three
when they all are equal — to diminish until one of the points <T, <T, £"'
is brought within the triangle a/3y.) In the first case we may say
that the tensions of the new surfaces are too small to be represented
by the distances of an internal point from the vertices of the triangle
representing the tensions of the original surfaces (or, for brevity,
that they are too small to be represented as in figure 15); in the
second case we may say that they are too great to be thus represented.
In the first case, the sum of the angles in each of the triangles adb,
bdc, cda is less than two right angles (compare figures 14 and 16) ;
292 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
in the second case, each pair of the triangles a/3<T', /3y<5', ya<T will
overlap, at least when the tensions crDA, <TDB, O"DO are only a little too
great to be represented as in figure 15, and the sum of the angles of
each of the triangles adb, bdc, cda will be greater than two right
angles.
Let us denote by i>A, VE, VG the portions of VD which were originally
occupied by the masses A, B, C, respectively, by SDA, SDB, SDC, the
areas of the surfaces specified per unit of length of the mass D,
and by SAB, SBO, SOA, the areas of the surfaces specified which were
replaced by the mass D per unit of its length. In numerical value,
^A> vv> vc wiH be equal to the areas of the curvilinear triangles
bed, cad, abd', and SDA, SDB> SDC> SAB, SBC, SCA to the lengths of the
lines be, ca, ab, cd, ad, bd. Also let
^s = °"DA SDA + °"DB SDB + crDC sDc — <jAB SAB — crBC SBC — crCA SCA, (626)
and Wv=p»vI>-pAyi.-pxVB-pGv0. (627)
The general condition of mechanical equilibrium for a system of
homogeneous masses not influenced by gravity, when the exterior
of the whole system is fixed, may be written
2(<r&)-Z(patO»0. (628)
(See (606).) If we apply this both to the original system consisting
of the masses A, B, and C, and to the system modified by the
introduction of the mass D, and take the difference of the results,
supposing the deformation of the system to be the same in each
case, we shall have
O"DA ^DA "I" tf'DB <^DB H~ °"DC O^DC — <TAB OSAB — <TBo OSB0
- <7CA &OA -Pi> &>D +PA SvA +pE SvB +pG 8vc = 0. (629)
In view of this relation, if we differentiate (626) and (627) regarding
all quantities except the pressures as variable, we obtain
d W s — d Wy = SDA do-DA + SDB ^DB + sDc ^DO
— SAB <^o-AB — SBC ^O"BC — SCA ^O"CA • (630)
Let us now suppose the system to vary in size, remaining always
similar to itself in form, and that the tensions diminish in the
same ratio as lines, while the pressures remain constant. Such
changes will evidently not impair the equilibrium. Since all the
quantities SDA, o-DA, SDB, <rDB, etc. vary in the same ratio,
SDA^DA^^DASDA), sDBdo-DB = Jd(<rDBsDB), etc. (631)
We have therefore by integration of (630)
TT8 — "^v = i (°"DA SDA + <TDB SDB + O-DO SDC — O*AB SAB — CTBO SBO — ^OASCA)* (632)
whence, by (626),
(633)
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 293
The condition of stability for the system when the pressures and
tensions are regarded as constant, and the position of the surfaces
A-B, B-C, C-A as fixed, is that W8— Wy shall be a minimum under
the same conditions. (See (549).) Now for any constant values of
the tensions and of pA, p*,pc> w^ may make i>D so small that when
it varies, the system remaining in equilibrium (which will in general
require a variation of ^D), we may neglect the curvatures of the
lines da, db, dc, and regard the figure abed as remaining similar
to itself. For the total curvature (i.e., the curvature measured in
degrees) of each of the lines ab, be, ca may be regarded as constant,
being equal to the constant difference of the sum of the angles of
one of the curvilinear triangles adb, bdc, cda and two right angles.
Therefore, when VD is very small, and the system is so deformed
that equilibrium would be preserved if jpD had the proper variation,
but this pressure as well as the others and all the tensions remain
constant, WB will vary as the lines in the figure abed, and TTV as
the square of these lines. Therefore, for such deformations,
This shows that the system cannot be stable for constant pressures
and tensions when VD is small and TFV is positive, since WB — Wy
will not be a minimum. It also shows that the system is stable
when TFV is negative. For, to determine whether W8 — TFV is a
minimum for constant values of the pressures and tensions, it will
evidently be sufficient to consider such varied forms of the system
as give the least value to W8 — Wv for any value of Vj> in connection
with the constant pressures and tensions. And it may easily be
shown that such forms of the system are those which would
preserve equilibrium if p^ had the proper value.
These results will enable us to determine the most important
questions relating to the stability of a line along which three
homogeneous fluids A, B, C meet, with respect to the formation of
a different fluid D. The components of D must of course be such
as are found in the surrounding bodies. We shall regard p^ and
°"DA> O"DB> O-DO as determined by that phase of D which satisfies
the conditions of equilibrium with the other bodies relating to
temperature and the potentials. These quantities are therefore
determinable, by means of the fundamental equations of the mass
D and of the surfaces D-A, D-B, D-C, from the temperature and
potentials of the given system.
Let us first consider the case in which the tensions, thus deter-
mined, can be represented as in figure 15, and pD has a value
consistent with the equilibrium of a small mass such as we have
been considering. It appears from the preceding discussion that
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
when i>D is sufficiently small the figure abed may be regarded as
rectilinear, and that its angles are entirely determined by its
tensions. Hence the ratios of t>A, i>B, v0, VD, for sufficiently small
values of VD, are determined by the tensions alone, and for con-
venience in calculating these ratios, we may suppose pA, pE, pc to
be equal, which will make the figure abed absolutely rectilinear,
and make £>D equal to the other pressures, since it is supposed that
this quantity has the value necessary for equilibrium. We may
obtain a simple expression for the ratios of v±, i>B, v0t VD in terms
of the tensions in the following manner. We shall write [DBC],
[DCA], etc., to denote the areas of triangles having sides equal to
the tensions of the surfaces between the masses specified.
v± : VB : triangle bdc : triangle adc
: be sin bed : ac sin acd
: sin bac sin bed : sin abc sin acd
: sin y8/3 sin Sa/3 : sin y8a sin
: sin yS@ 8/3 : sin ySa So.
: triangle yS/3 : triangle ySa
: [DBC] : [DCA].
a
Hence,
where
v0 : v» :: [DEC] : [DCA] : [DAB] : [ABC], (634)
may be written for [ABC], and analogous expressions for the, other
symbols, the sign ^/ denoting the positive root of the necessarily
positive expression which follows. This proportion will hold true
in any case of equilibrium, when the tensions satisfy the condition
mentioned and v^ is sufficiently small. Now if PA—PE—PC> PD
will have the same value, and we shall have by (627) TTV = 0, and
by (633) TFg = 0. But when VD is very small, the value of Ws is
entirely determined by the tensions and VD. Therefore, whenever
the tensions satisfy the condition supposed, and V-Q is very small
(whether pA, pE, pc are equal or unequal),
0 = W g = Fv =^D^D -PA^A -Psv* -pGvG, (635)
which with (634) gives
+ [DAB] Po
[DBC] + [DCA] + [DAB]
(636)
Since this is the only value of £>D for which equilibrium is possible
when the tensions satisfy the condition supposed and v^ is small,
it follows that when £>D has a less value, the line where the fluids
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 295
A, B, C meet is stable with respect to the formation of the fluid D.
When pD has a greater value, if such a line can exist at all, it must
be at least practically unstable, i.e., if only a very small mass of
the fluid D should be formed it would tend to increase.
Let us next consider the case in which the tensions of the new
surfaces are too small to be represented as in figure 15. If the
pressures and tensions are consistent with equilibrium for any very
.small value of VD, the angles of each of the curvilinear triangles
adb, bdc, cda will be together less than two right angles, and the
lines ab, be, ca will be convex toward the mass D. For given
values of the pressures and tensions, it will be easy to determine
the magnitude of VD. For the tensions will give the total curvatures
(in degrees) of the lines ab, be, ca; and the pressures will give
the radii of curvature. These lines are thus completely determined.
In order that v^ shall be very small it is evidently necessary that
Pv shall be less than the other pressures. Yet if the tensions of
the new surfaces are only a very little too small to be represented
as in figure 15, VD may be quite small when the value of £>D is only
<a little less than that given by equation (636). In any case, when
the tensions of the new surfaces are too small to be represented as
in figure 15, and v^ is small, TFV is negative, and the equilibrium
of the mass D is stable. Moreover, WB — Wy, which represents the
work necessary to form the mass D with its surfaces in place of
the other masses and surfaces, is negative.
With respect to the stability of a line in which the surfaces A-B,
B-C, C-A meet, when the tensions of the new surfaces are too
small to be represented as in figure 15, we first observe that when
the pressures and tensions are such as to make VD moderately small
but not so small as to be neglected (this will be when p^ is some-
what smaller than the second member of (636), — more or less smaller
according as the tensions differ more or less from such as are repre-
sented in figure 15), the equilibrium of such a line as that supposed
(if it is capable of existing at all) is at least practically unstable.
For greater values of _pD (with the same values of the other pressures
and the tensions) the same will be true. For somewhat smaller
values of £>D, the mass of the phase D which will be formed will be
so small, that we may neglect this mass and regard the surfaces
A-B, B-C, C-A as meeting in a line in stable equilibrium. For still
smaller values of p^ , we may likewise regard the surfaces A-B, B-C,
C-A as capable of meeting in stable equilibrium. It may be observed
that when t>D, as determined by our equations, becomes quite insensible,
the conception of a small mass D having the properties deducible
from our equations ceases to be accurate, since the matter in the
vicinity of a line where these surfaces of discontinuity meet must be
296 EQUILIBKIUM OF HETEKOGENEOUS SUBSTANCES.
in a peculiar state of equilibrium not recognized by our equations.*"
But this cannot affect the validity of our conclusion with respect ta
the stability of the line in question.
The case remains to be considered in which the tensions of the
new surfaces are too great to be represented as in figure 15. Let us
suppose that they are not very much too great to be thus represented.
When the pressures are such as to make VD moderately small (in case
of equilibrium) but not so small that the mass D to which it relates
ceases to have the properties of matter in mass (this will be when
Pv is somewhat greater than the second member of (636), — more or
less greater according as the tensions differ more or less from such as
are represented in figure 15), the line where the surfaces A-B, B-C,
C-A meet will be in stable equilibrium with respect to the formation
of such a mass as we have considered, since W8 — Wy will be positive.
The same will be true for less values of _pD. For greater values of p^r
the value of Ws — TTY, which measures the stability with respect to
the kind of change considered, diminishes. It does not vanish, accord-
ing to our equations, for finite values of ^D. But these equations are
not to be trusted beyond the limit at which the mass D ceases to be
of sensible magnitude.
But when the tensions are such as we now suppose, we must also
consider the possible formation of a mass D within a closed figure in
which the surfaces D-A, D-B, D-C meet together (with the surfaces
A-B, B-C, C-A) in two opposite points. If such a figure is to be in
equilibrium, the six tensions must be such as can be represented by
the six distances of four points in space (see pages 288, 289),— a con-
dition which evidently agrees with the supposition which we have
made. If we denote by wv the work gained in forming the mass D (of
such size and form as to be in equilibrium) in place of the other masses,
and by wa the work expended in forming the new surfaces in place of
the old, it may easily be shown by a method similar to that used on
page 292 that w8 = %wy. From this we obtain wa — wv = ^wy. This
is evidently positive when £>D is greater than the other pressures.
But it diminishes writh increase of jpD, as easily appears from the
* See note on page 288. We may here add that the linear tension there mentioned
may have a negative value. This would be the case with respect to a line in which
three surfaces of discontinuity are regarded as meeting, but where nevertheless there
really exists in stable equilibrium a filament of different phase from the three sur-
rounding masses. The value of the linear tension for the supposed line, would be
nearly equal to the value of Ws- Wv for the actually existing filament. (For the
exact value of the linear tension it would be necessary to add the sum of the linear
tensions of the three edges of the filament.) We may regard two soap-bubbles
adhering together as an example of this case. The reader will easily convince himself
that in an exact treatment of the equilibrium of such a double bubble we must
recognize a certain negative tension in the line of intersection of the three surfaces
of discontinuity.
EQUILIBEIUM OF HETEKOGENEOUS SUBSTANCES. 297
equivalent expression %wa. Hence the line of intersection of the
surfaces of discontinuity A-B, B-C, C-A is stable for values of
greater than the other pressures (and therefore for all values of
so long as our method is to be regarded as accurate, which will be so
long as the mass D which would be in equilibrium has a sensible size.
In certain cases in which the tensions of the new surfaces are much
too large to be represented as in figure 15, the reasoning of the two
last paragraphs will cease to be applicable. These are cases in which
the six tensions cannot be represented by the sides of a tetrahedron.
It is not necessary to discuss these cases, which are distinguished by
the different shape which the mass D would take if it should be
formed, since it is evident that they can constitute no exception to
the results which we have obtained. For an increase of the values
of o-DA, <rDB, <TDC cannot favor the formation of D, and hence cannot
impair the stability of the line considered, as deduced from our equa-
tions. Nor can an increase of these tensions essentially affect .the
fact that the stability thus demonstrated may fail to be realized when
Pv is considerably greater than the other pressures, since the a priori
demonstration of the stability of any one of the surfaces A-B, B-C, C-A,
taken singly, is subject to the limitation mentioned. (See pages
261, 262.)
The Condition of Stability for Fluids relating to the Formation of
a New Phase at a Point where the Vertices of Four Different
Masses meet.
Let four different fluid masses A, B, C, D meet about a point, so as
to form the six surfaces of discontinuity A-B, B-C, C-A, D-A, D-B,
D-C, which meet in the four lines A-B-C, B-C-D, C-D-A, D-A-B, these
lines meeting in the vertical point. Let us suppose the system stable in
other respects, and consider the conditions of stability for the vertical
point with respect to the possible formation of a different fluid mass E.
If the system can be in equilibrium when the vertical point has
been replaced by a mass E against which the four masses A, B, C, D
abut, being truncated at their vertices, it is evident that E will have
four vertices, at each of which six surfaces of discontinuity meet.
(Thus at one vertex there will be the surfaces formed by A, B, C,
and E.) The tensions of each set of six surfaces (like those of the
six surfaces formed by A, B, C, and D) must therefore be such that
they can be represented by the six edges of a tetrahedron. When
the tensions do not satisfy these relations, there will be no particular
condition of stability for the point about which A, B, C, and D meet,
since if a mass E should be formed, it would distribute itself along
some of the lines or surfaces which meet at the vertical point, and it
298 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
is therefore sufficient to consider the stability of these lines and sur-
faces. We shall suppose that the relations mentioned are satisfied.
If we denote by Wy the work gained in forming the mass E (of
such size and form as to be in equilibrium) in place of the portions
of the other masses which are suppressed, and by W8 the work ex-
pended in forming the new surfaces in place of the old, it may easily
be shown by a method similar to that used on page 292 that
Fs = fTFv, (637)
whence TF8- Fv = iTTv; (638)
also, that when the volume E is small, the equilibrium of E will be
stable or unstable according as W8 and Wv are negative or positive.
A critical relation for the tensions is that which makes equilibrium
possible for the system of the five masses A, B, C, D, E, when all
the surfaces are plane. The ten tensions may then be represented in
magnitude and direction by the ten distances of five points in space
a, /3, y, 8, e, viz., the tension of A-B and the direction of its normal
by the line a/5, etc. The point e will lie within the tetrahedron
formed by the other points. If we write VE for the volume of E, and
VA, VB, vc, V-D for the volumes of the parts of the other masses which
are suppressed to make room for E, we have evidently
Wy =pEvE -p&y± -pEvB -p0vG -PDVD . (639)
Hence, when all the surfaces are plane, TFV = 0, and TFg = 0. Now
equilibrium is always possible for a given small value of VE with any
given values of the tensions and of p±, pB, p0) p^. When the tensions
satisfy the critical relation, TTS = 0, if pA=ps=pG—pI). But when
t»E is small and constant, the value of Ws must be independent of
PA> PE> Pc> Pv> since the angles of the surfaces are determined by the
tensions and their curvatures may be neglected. Hence, TFg = 0, and
Wy = 0, when the critical relation is satisfied and VE small. This gives
= VAPA + VBPB + VcPc + v^Py (640)
^E
In calculating the ratios of i>A, i>B, VG, VD, i>E, we may suppose all the
surfaces to be plane. Then E will have the form of a tetrahedron,
the vertices of which may be called a, b, c, d (each vertex being
named after the mass which is not found there), and VA, VE, vc> V-Q will
be the volumes of the tetrahedra into which it may be divided
by planes passing through its edges and an interior point e. The
volumes of these tetrahedra are proportional to those of the five
tetrahedra of the figure afiySe, as will easily appear if we recollect
that the line ab is common to the surfaces C-D, D-E, E-C, and there-
fore perpendicular to the surface common to the lines yS, Se, ey, i.e.
to the surface y<$e, and so in other cases (it will be observed that
-y, S, and e are the letters which do not correspond to a or b) ; also
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 299
that the surface abc is the surface D-E and therefore perpendicular
to Se, etc. Let tetr abed, trian abc, etc. denote the volume of the
tetrahedron or the area of the triangle specified, sin(ab, be),
sin (abc, dbc), sin (abc, ad), etc. the sines of the angles made by the
lines and surfaces specified, and [BCDE], [CDEA], etc. the volumes
of tetrahedra having edges equal to the tensions of the surfaces
between the masses specified. Then, since we may express the
volume of a tetrahedron either by ^ of the product of one side, an
edge leading to the opposite vertex, and the sine of the angle which
these make, or by f of the product of two sides divided by the
common edge and multiplied by the sine of the included angle,
tetr bcde : tetr acde
be sin (be, cde) : ac sin (ac, cde)
sin (ba, ac) sin (be, cde) : sin (ab, be) sin (ac, cde)
sin (ySe, PSe) sin (aSe, a/3) : sin (ySe, aSe) sin (/3(Se, a/8)
tetr yPSe tetr paSe tetr ya Se tetr apSe
trian pSe trian aSe ' trian aSe trian pSe
tetr ypSe : tetr yaSe
[BCDE]: [CD KA].
Hence,
VA : VE : v0 : v» : : [BCDE] : [CDEA] : [DEAB] : [EABC], (641)
and (640) may be written
_
[BCDE] + [CDEA] + [DEAB] + [EABC]
If the value of pE is less than this, when the tensions satisfy the critical
relation, the point where vertices of the masses A, B, C, D meet is
stable with respect to the formation of any mass of the nature of E.
But if the value of pE is greater, either the masses A, B, C, D cannot
meet at a point in equilibrium, or the equilibrium will be at least
practically unstable.
When the tensions of the new surfaces are too small to satisfy the
critical relation with the other tensions, these surfaces will be convex
toward E ; when their tensions are too great for that relation, the
surfaces will be concave toward E. In the first case, TFV is negative,
and the equilibrium of the five masses A, B, C, D, E is stable, but the
equilibrium of the four masses A, B, C, D meeting at a point is
impossible or at least practically unstable. This is subject to the
limitation that when pE is sufficiently small the mass E which will
form will be so small that it may be neglected. This will only be
the case when pE is smaller — in general considerably smaller — than
the second member of (642). In the second case, the equilibrium
of the five masses A, B, C, D, E will be unstable, but the equilibrium
300 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
of the four masses A, B, C, D will be stable unless VE (calculated for
the case of the five masses) is of insensible magnitude. This will
only be the case when pE is greater — in general considerably greater —
than the second member of (642).
Liquid Films.
When a fluid exists in the form of a thin film between other fluids,
the great inequality of its extension in different directions will give
rise to certain peculiar properties, even when its thickness is sufficient
for its interior to have the properties of matter in mass. The fre-
quent occurrence of such films, and the remarkable properties which
they exhibit, entitle them to particular consideration. To fix our
ideas, we shall suppose that the film is liquid and that the contiguous
fluids are gaseous. The reader will observe our results are not
dependent, so far as their general character is concerned, upon this
supposition.
Let us imagine the film to be divided by surfaces perpendicular to
its sides into small portions of which all the dimensions are of the
same order of magnitude as the thickness of the film, — such portions
to be called elements of the film, — it is evident that far less time will
in general be required for the attainment of approximate equilibrium
between the different parts of any such element and the other fluids
which are immediately contiguous, than for the attainment of equi-
librium between all the different elements of the film. There will
accordingly be a time, commencing shortly after the formation of the
film, in which its separate elements may be regarded as satisfying
the conditions of internal equilibrium, and of equilibrium with the
contiguous gases, while they may not satisfy all the conditions of
equilibrium with each other. It is when the changes due to this want
of complete equilibrium take place so slowly that the film appears to
be at rest, except so far as it accommodates itself to any change in
the external conditions to which it is subjected, that the characteristic
properties of the film are most striking and most sharply defined.
Let us therefore consider the properties which will belong to a film
sufficiently thick for its interior to have the properties of matter in
mass, in virtue of the approximate equilibrium of all its elements
taken separately, when the matter contained in each element is
regarded as invariable, with the exception of certain substances
which are components of the contiguous gas-masses and have their
potentials thereby determined. The occurrence of a film which pre-
cisely satisfies these conditions may be exceptional, but the discussion
of this somewhat ideal case will enable us to understand the principal
laws which determine the behavior of liquid films in general.
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 301
Let us first consider the properties which will belong to each
element of the film under the conditions mentioned. Let us suppose
the element extended, while the temperature and the potentials
which are determined by the contiguous gas-masses are unchanged.
If the film has no components except those of which the potentials
are maintained constant, there will be no variation of tension in its
surfaces. The same will be true when the film has only one com-
ponent of which the potential is not maintained constant, provided
that this is a component of the interior of the film and not of its sur-
face alone. If we regard the thickness of the film as determined by
dividing surfaces which make the surface-density of this component
vanish, the thickness will vary inversely as the area of the element
of the film, but no change will be produced in the nature or the ten-
sion of its surfaces. If, however, the single component of which the
potential is not maintained constant is confined to the surfaces of the
film, an extension of the element will generally produce a decrease in
the potential of this component, and an increase of tension. This will
certainly be true in those cases in which the component shows a ten-
dency to distribute itself with a uniform superficial density.
When the film has two or more components of which the potentials
are not maintained constant by the contiguous gas-masses, they will
not in general exist in the same proportion in the interior of the
film as on its surfaces, but those components which diminish the
tensions will be found in greater proportion on the surfaces. When
the film is extended, there will therefore not be enough of these
substances to keep up the same volume- and surface-densities as
before, and the deficiency will cause a certain increase of tension.
The value of the elasticity of the film (i.e., the infinitesimal increase
of the united tensions of its surfaces divided by the infinitesimal
increase of area in a unit of surface) may be calculated from the
quantities which specify the nature of the film, when the funda-
mental equations of the interior mass, of the contiguous gas-masses,
and of the two surfaces of discontinuity are known. We may
illustrate this by a simple example.
Let us suppose that the two surfaces of a plane film are entirely
alike, that the contiguous gas-masses are identical in phase, and
that they determine the potentials of all the components of the
film except two. Let us call these components S1 and S2, the latter
denoting that which occurs in greater proportion on the surface
than in the interior of the film. Let us denote by yl and y2 the
densities of these components in the interior of the film, by X
the thickness of the film determined by such dividing surfaces as
make the surface-density of Si vanish (see page 234), by r2(1) the
surface-density of the other component as determined by the same
302 EQUILIBKIUM OF HETEROGENEOUS SUBSTANCES.
surfaces, by <r and s the tension and area of one of these surfaces,
and by E the elasticity of the film when extended under the
supposition that the total quantities of $x and $2 in the part of
the film extended are invariable, as also the temperature and the
potentials of the other components. From the definition of E we
have
da
2do- = E—> (643)
8
and from the conditions of the extension of the film
ds=
s
Hence we obtain
—
ds
+ 2r2(1))— = -
o
and eliminating d\,
ds
2yir2(1)— = -Xy1c?y2 + Xy2c?y1-2y1^r2(1). (645)
o
If we set r = *a, (646)
we have dr = ~*, (647)
Vi
d*
and 2r2(1)— =-Xy1dr-2dr2{1). « (648)
s
With this equation we may eliminate ds from (643). We may also
eliminate do- by the necessary relation (see (514))
d(T= — 1^2
This will give
4r2(1)2 dft = E(\7ldr + 2 c£T2(1)), (649)
or
where the differential coefficients are to be determined on the con-
ditions that the temperature and all the potentials except //1 and /z2
are constant, and that the pressure in the interior of the film
shall remain equal to that in the contiguous gas-masses. The latter
condition may be expressed by the equation
(ri - y/)^ + (y2 - y2')^2 = o, (651 )
in which y^ and y4/ denote the densities of 8l and $2 in the con-
tiguous gas-masses. (See (98).) When the tension of the surfaces
of the film and the pressures in its interior and in the contiguous
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 303
gas -masses are known in terras of the temperature and potentials,
equation (650) will give the value of E in terms of the same
variables together with X.
If we write Gl and Gz for the total quantities of 8l and 82 per
unit of area of the film, we have
Therefore,
(652)
(653)
(654)
where the differential coefficients in the second member are to be
determined as in (650), and that in the first member with the
additional condition that G1 is constant. Therefore,
E
, (655)
the last differential coefficient being determined by the same condi-
tions as that in the preceding equation. It will be observed that the
value of E will be positive in any ordinary case.
These equations give the elasticity of any element of the film
when the temperature and the potentials for the substances which
are found in the contiguous gas-masses are regarded as constant,
and the potentials for the other components, //1 and /z2, have had
time to equalize themselves throughout the element considered. The
increase of tension immediately after a rapid extension will be greater
than that given by these equations.
The existence of this elasticity, which has thus been established
from a priori considerations, is clearly indicated by the phenomena
which liquid films present. Yet it is not to be demonstrated simply
by comparing the tensions of films of different thickness, even when
they are made from the same liquid, for difference of thickness does
not necessarily involve any difference of tension. When the phases
within the films as well as without are the same, and the surfaces of
the films are also the same, there will be no difference of tension.
Nor will the tension of the same film be altered, if a part of the
interior drains away in the course of time, without affecting the
surfaces. In case the thickness of the film is reduced by evapor-
ation, the tension may be either increased or diminished. (The
evaporation of the substance 8lt in the case we have just considered,
would diminish the tension.) Yet it may easily be shown that
304 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
extension increases the tension of a film and contraction diminishes
it. When a plane film is held vertically, the tension of the upper
portions must evidently be greater than that of the lower. The
tensions in every part of the film may be reduced to equality by
turning it into a horizontal position. By restoring the original
position we may restore the original tensions, or nearly so. It is
evident that the same element of the film is capable of supporting
very unequal tensions. Nor can this be always attributed to viscosity
of the film. For in many cases, if we hold the film nearly horizontal,
and elevate first one side and then another, the lighter portions of
the film will dart from one side to the other, so as to show a very
striking mobility in the film. The differences of tension which cause
these rapid movements are only a very small fraction of the difference
of tension in the upper and lower portions of the film when held
vertically.
If we account for the power of an element of the film to support
an increase of tension by viscosity, it will be necessary to suppose
that the viscosity offers a resistance to a deformation of the film in
which its surface is enlarged and its thickness diminished, which is
enormously great in comparison with the resistance to a deformation
in which the film is extended in the direction of one tangent and
contracted in the direction of another, while its thickness and the
areas of its surfaces remain constant. This is not to be readily
admitted as a physical explanation, although to a certain extent the
phenomena resemble those which would be caused by such a singular
viscosity. (See page 274.) The only natural explanation of the
phenomena is that the extension of an element of the film, which
is the immediate result of an increase of external force applied to
its perimeter, causes an increase of its tension, by which it is brought
into true equilibrium with the external forces.
The phenomena to which we have referred are such as are apparent
to a very cursory observation. In the following experiment, which
is described by M. Plateau,* an increased tension is manifested in a
film while contracting after a previous extension. The warmth of a
finger brought near to a bubble of soap-water with glycerine, which
is thin enough to show colors, causes a spot to appear indicating
a diminution of thickness. When the finger is removed, the spot
returns to its original color. This indicates a contraction, which
would be resisted by any viscosity of the film, and can only be due
to an excess of tension in the portion stretched, on the return of its
original temperature.
We have so far supposed that the film is thick enough for its
* Statique. expdrimentale et thdorique des liquides soumis aux seules forces moltculaires,
vol. i, p. 294.
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 305
interior to have the properties of matter in mass. Its properties are
then entirely determined by those of the three phases and the two
surfaces of discontinuity. From these we can also determine, in part
at least, the properties of a film at the limit at which the interior
ceases to have the properties of matter in mass. The elasticity of
the film, which increases with its thinness, cannot of course vanish
at that limit, so that the film cannot become unstable with respect
to extension and contraction of its elements immediately after passing
that limit.
Yet a certain kind of instability will probably arise, which we may
here notice, although it relates to changes in which the condition of
the invariability of the quantities of certain components in an
element of the film is not satisfied. With respect to variations in the
distribution of its components, a film will in general be stable, when
its interior has the properties of matter in mass, with the single
exception of variations affecting its thickness without any change of
phase or of the nature of the surfaces. With respect to this kind
of change, which may be brought about by a current in the interior of
the film, the equilibrium is neutral. But when the interior ceases to
have the properties of matter in mass, it is to be supposed that the
equilibrium will generally become unstable in this respect. For it is
not likely that the neutral equilibrium will be unaffected by such a
change of circumstances, and since the film certainly becomes unstable
when it is sufficiently reduced in thickness, it is most natural to
suppose that the first effect of diminishing the thickness will be in the
direction of instability rather than in that of stability. (We are here
considering liquid films between gaseous masses. In certain other
cases, the opposite supposition might be more natural, as in respect to
a tilm of water between mercury and air, which would certainly
become stable when sufficiently reduced in thickness.)
Let us now return to our former suppositions — that the film is thick
enough for the interior to have the properties of matter in mass, and
that the matter in each element is invariable, except with respect to
those substances which have their potentials determined by the
contiguous gas-masses — and consider what conditions are necessary
for equilibrium in such a case.
In consequence of the supposed equilibrium of its several elements,
such a film may be treated as a simple surface of discontinuity
between the contiguous gas-masses (which may be similar or different),
whenever its radius of curvature is very large in comparison with its
thickness, — a condition which we shall always suppose to be fulfilled.
With respect to the film considered in this light, the mechanical
conditions of equilibrium will always be satisfied, or very nearly so,
as soon as a state of approximate rest is attained, except in those
<i. I. U
306 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
cases in which the film exhibits a decided viscosity. That is, the
relation/* (618), (614), (615) will hold true, when by or we understand
the tension of the film regarded as a simple surface of discontinuity
(this is equivalent to the sum of the tensions of the two surfaces of
the film), and by I1 its mass per unit of area diminished by the mass
of gas which would occupy the same space if the film should be
suppressed and the gases should meet at its surface of tension. This
Hwfitce of tension of the film will evidently divide the distance
between the surfaces of tension for the two surfaces of the film
taken separately, in the inverse ratio of their tensions. For practical
purposes, we may regard F simply as the mass of the film per unit of
area. It will be observed that the terms containing F in (613) and
(614) are not to be neglected in our present application of these
equations.
But the mechanical conditions of equilibrium for the film regarded
us an approximately homogeneous mass in the form of a thin sheet
Unmded by two surfaces of discontinuity are not necessarily satisfied
when the film is in a state of apparent rest. In fact, these conditions
cannot be satisfied (in any place where the force of gravity has an
appreciable intensity) unless the film is horizontal. For the pressure
in the interior of the film cannot satisfy simultaneously condition
(612), which requires it to vary rapidly with the height 0, and
condition (613) applied separately to the different surfaces, which
makes it a certain mean between the pressures in the adjacent
gas-masses. Nor can these conditions be deduced from the general
condition of mechanical equilibrium (606) or (611), without supposing
that the interior of the film is free to move independently of the
surfaces, which is contrary to what we have supposed.
Moreover, the potentials of the various components of the film
will not in general satisfy conditions (617), and cannot (when the
temperature is uniform) unless the film is horizontal. For if these
conditions were satisfied, equation (612) would follow as a consequence.
(See page 283.)
We may here remark that such a film as we are considering cam
form any exception to the principle indicated on page 284, — thai
when a surface of discontinuity which satisfies the conditions
mechanical equilibrium has only one component which is not foun<
in the contiguous masses, and these masses satisfy all the conditioi
of equilibrium, the potential for the component mentioned must satisfy
the law expressed in (617), as a consequence of the condition ol
mechanical equilibrium (614). Therefore, as we have just seen that
it is impossible that all the potentials in a liquid film which is n<
horizontal should conform to (617) when the temperature is unifoi
it follows that if a liquid film exhibits any persistence which
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 307
not due to viscosity, or to a horizontal position, or to differences of
temperature, it must have more than one component of which the
potential is not determined by the contiguous gas- masses in accordance
with (617).
The difficulties of the quantitative experimental verification of the
properties which have been described would be very great, even in
cases in which the conditions we have imagined were entirely
fulfilled. Yet the general effect of any divergence from these
conditions will be easily perceived, and when allowance is made for
such divergence, the general behavior of liquid films will be seen to
agree with the requirements of theory.
The formation of a liquid film takes place most symmetrically
when a bubble of air rises to the top of a mass of the liquid. The
motion of the liquid, as it is displaced by the bubble, is evidently
Huch as to stretch the two surfaces in which the liquid meets the air,
where these surfaces approach one another. This will cause "an
increase of tension, which will tend to restrain the extension of the
surfaces. The extent to which this effect is produced will vary with
the nature of the liquid. Let us suppose that the case is one in
which the liquid contains one or more components which, although
constituting but a very small part of its mass, greatly reduce its
tension. Such components will exist in excess on the surfaces of the
liquid. In this case the restraint upon the extension of the surfaces
will be considerable, and as the bubble of air rises above the general
level of the liquid, the motion of the latter will consist largely of a
running out from between the two surfaces. But this running out of
Um liquid will be greatly retarded by its viscosity as soon as it is
reduced to tlm thickness of a film, arid Uio nH'w.t of Ui«; ^xf^nsion of
tlm surfaces in increasing their tension will become greater and
more permanent as the quantity of liquid diminishes which is
available for supplying the substances which go to form the increased
surfaces.
We may form a rough estimate of the amount of motion which is
possible for the interior of a liquid film, relatively to its exterior, by
calculating the descent of water between parallel vertical planes at
which the motion of the water is reduced to zero. If we use the
coefficient of viscosity as determined by Helmholtz and Piotrowski,*
we obtain - 7=5811>!j (656)
where V denotes the mean velocity of the water (i.e., that velocity
* Sitzunfftberichte der Wiener A kademie (mathemat.-naiurunwi. Clause), B. xl, H. 007.
Tli*! calculation of formula (65fi) and that of the factor (fl) applied to the formula of
PoiHOuille, to adapt it to a current between plane HurfaocH, have been made by meaiut
of the general equation!) of the motion of a VIBOOIUI liquid OH given in the memoir
referred to.
308 EQUILIBKIUM OF HETEEOGENEOUS SUBSTANCES.
which, if it were uniform throughout the whole space between the
fixed planes, would give the same discharge of water as the actual
variable velocity) expressed in millimeters per second, and D denotes
the distance in millimeters between the fixed planes, which is
supposed to be very small in proportion to their other dimensions.
This is for the temperature of 24*5° C. For the same temperature,
the experiments of Poiseuille * give
F=337D2
for the descent of water in long capillary tubes, which is equivalent to
F=899D2 (657)
for descent between parallel planes. The numerical coefficient in this
equation differs considerably from that in (656), which is derived from
experiments of an entirely different nature, but we may at least
conclude that in a film of a liquid which has a viscosity and specific
gravity not very different from those of water at the temperature
mentioned the mean velocity of the interior relatively to the surfaces
will not probably exceed 1000 D2. This is a velocity of "lmm per
second for a thickness of 'Olmm, '06mm per minute for a thickness of
•001 (which corresponds to the red of the fifth order in a film of
water), and -036mm per hour for a thickness of '0001mm (which
corresponds to the white of the first order). Such an internal current
is evidently consistent with great persistence of the film, especially in
those cases in which the film can exist in a state of the greatest
tenuity. On the other hand, the above equations give so large a
value of V for thicknesses of lmm or -lmm} that the film can evidently
be formed without carrying up any great weight of liquid, and any
such thicknesses as these can have only a momentary existence.
A little consideration will show that the phenomenon is essentially
of the same nature when films are formed in any other way, as by
dipping a ring or the mouth of a cup in the liquid and then
withdrawing it. When the film is formed in the mouth of a pipe, it
may sometimes be extended so as to form a large bubble. Since the
elasticity (i.e., the increase of the tension with extension) is greater in
the thinner parts, the thicker parts will be most extended, and the
effect of this process (so far as it is not modified by gravity) will be
to diminish the ratio of the greatest to the least thickness of the
film. During this extension, as well as at other times, the increased
elasticity due to imperfect communication of heat, etc., will serve to
protect the bubble from fracture by shocks received from the air or
the pipe. If the bubble is now laid upon a suitable support, the
condition (613) will be realized almost instantly. The bubble will
* Ibid. , p. 653 ; or Mtmoirea des Savants fitrangers, vol. ix, p. 532.
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 309
then tend toward conformity with condition (614), the lighter portions
rising to the top, more or less slowly, according to the viscosity of the
film. The resulting difference of thickness between the upper and
the lower parts of the bubble is due partly to the greater tension
to which the upper parts are subject, and partly to a difference in
the matter of which they are composed. When the film has only
two components of which the potentials are not determined by the
contiguous atmosphere, the laws which govern the arrangement of the
elements of the film may be very simply expressed. If we call these
components Sl and $2, the latter denoting (as on page 301) that
which exists in excess at the surface, one element of the film will tend
toward the same level with another, or a higher, or a lower level,
according as the quantity of 82 bears the same ratio to the quantity
of S1 in the first element as in the second, or a greater, or a less ratio.
When a film, however formed, satisfies both the conditions (613)
and (614), its thickness being sufficient for its interior to have the
properties of matter in mass, the interior will still be subject to the
slow current which we have already described, if it is truly fluid,
however great its viscosity may be. It seems probable, however,
that this process is often totally arrested by a certain gelatinous
consistency of the mass in question, in virtue of which, although
practically fluid in its behavior with reference to ordinary stresses,
it may have the properties of a solid with respect to such very
small stresses as those which are caused by gravity in the interior
of a very thin film which satisfies the conditions (613) and (614).
However this may be, there is another cause which is often more
potent in producing changes in a film, when the conditions just
mentioned are approximately satisfied, than the action of gravity on
its interior. This will be seen if we turn our attention to the edge
where the film is terminated. At such an edge we generally find a
liquid mass, continuous in phase with the interior of the film, which
is bounded by concave surfaces, and in which the pressure is therefore
less than in the interior of the film. This liquid mass therefore
exerts a strong suction upon the interior of the film, by which its
thickness is rapidly reduced. This effect is best seen when a film
which has been formed in a ring is held in a vertical position. Unless
the film is very viscous, its diminished thickness near the edge causes
a rapid upward current on each side, while the central portion slowly
descends. Also at the bottom of the film, where the edge is nearly
horizontal, portions which have become thinned escape from their
position of unstable equilibrium beneath heavier portions, and pass
upwards, traversing the central portion of the film until they find a
position of stable equilibrium. By these processes, the whole film is
rapidly reduced in thickness.
310 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
The energy of the suction which produces these effects may be
inferred from the following considerations. The pressure in the
slender liquid mass which encircles the film is of course variable,
being greater in the lower portions than in the upper, but it is
everywhere less than the pressure of the atmosphere. Let us take
a point where the pressure is less than that of the atmosphere by an
amount represented by a column of the liquid one centimeter in height.
(It is probable that much greater differences of pressure occur.) At a
point near by in the interior of the film the pressure is that of the
atmosphere. Now if the difference of pressure of these two points
were distributed uniformly through the space of one centimeter, the
intensity of its action would be exactly equal to that of gravity.
But since the change of pressure must take place very suddenly
(in a small fraction of a millimeter), its effect in producing a current
in a limited space must be enormously great compared with that of
gravity.
Since the process just described is connected with the descent of
the liquid in the mass encircling the film, we may regard it as
another example of the downward tendency of the interior of the
film. There is a third way in which this descent may take place,
when the principal component of the interior is volatile, viz.,
through the air. Thus, in the case of a film of soap-water, if we
suppose the atmosphere to be of such humidity that the potential for
water at a level mid- way between the top and bottom of the film has
the same value in the atmosphere as in the film, it may easily be
shown that evaporation will take place in the upper portions and
condensation in the lower. These processes, if the atmosphere were
otherwise undisturbed, would occasion currents of diffusion and other
currents, the general effect of which would be to carry the moisture
downward. Such a precise adjustment would be hardly attainable,
and the processes described would not be so rapid as to have a
practical importance.
But when the potential for water in the atmosphere differs con-
siderably from that in the film, as in the case of a film of soap -water
in a dry atmosphere, or a film of soap- water with glycerine in a moist
atmosphere, the effect of evaporation or condensation is not to be
neglected. In the first case, the diminution of the thickness of the
film will be accelerated, in the second, retarded. In the case of the
film containing glycerine, it should be observed that the water con-
densed cannot in all respects replace the fluid carried down by the
internal current but that the two processes together will tend to
wash out the glycerine from the film.
But when a component which greatly diminishes the tension of the
film, although forming but a small fraction of its mass (therefore
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 311
existing in excess at the surface), is volatile, the effect of evaporation
and condensation may be considerable, even when the mean value of
the potential for that component is the same in the film as in the sur-
rounding atmosphere. To illustrate this, let us take the simple case
of two components 8l and S2, as before. (See page 301.) It appears
from equation (508) that the potentials must vary in the film with
the height z, since the tension does, and from (98) that these varia-
tions must (very nearly) satisfy the relation
*• (658)
•/! and y2 denoting the densities of 8^ and S2 in the interior of the
film. The variation of the potential of S2 as we pass from one level
to another is therefore as much more rapid than that of 8lt as its
density in the interior of the film is less. If then the resistances
restraining the evaporation, transmission through the atmosphere,
and condensation of the two substances are the same, these processes
will go on much more rapidly with respect to S2. It will be observed
that the values of ~-1 and - will have opposite signs, the tendency
of S1 being to pass down through the atmosphere, and that of S2 to
pass up. Moreover, it may easily be shown that the evaporation or
condensation of $2 will produce a very much greater effect than the
evaporation or condensation of the same quantity of 8r These effects
are really of the same kind. For if condensation of $2 takes place at
the top of the film, it will cause a diminution of tension, and thus
occasion an extension of this part of the film, by which its thickness
will be reduced, as it would be by evaporation of 8r We may infer
that it is a general condition of the persistence of liquid films, that the
substance which causes the diminution of tension in the lower parts of
the film must not be volatile.
But apart from any action of the atmosphere, we have seen that a
film which is truly fluid in its interior is in general subject to a con-
tinual diminution of thickness by the internal currents due to gravity
and the suction at its edge. Sooner or later, the interior will some-
where cease to have the properties of matter in mass. The film will
then probably become unstable with respect to a flux of the interior
(see page 305), the thinnest parts tending to become still more thin
(apart from any external cause) very much as if there were an attrac-
tion between the surfaces of the film, insensible at greater distances,
but becoming sensible when the thickness of the film is sufficiently
reduced. We should expect this to determine the rupture of the film,
and such is doubtless the case with most liquids. In a film of soap-
water, however, the rupture does not take place, and the processes
312 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
which go on can be watched. It is apparent even to a very superficial
observation that a film of which the tint is approaching the black
exhibits a remarkable instability. The continuous change of tint is
interrupted by the breaking out and rapid extension of black spots.
That in the formation of these black spots a separation of different
substances takes place, and not simply an extension of a part of the
film, is shown by the fact that the film is made thicker at the edge of
these spots.
This is very distinctly seen in a plane vertical film, when a single
black spot breaks out and spreads rapidly over a considerable area
which was before of a nearly uniform tint approaching the black. The
edge of the black spot as it spreads is marked as it were by a string of
bright beads, which unite together on touching, and thus becoming
larger, glide down across the bands of color below. Under favorable
circumstances, there is often quite a shower of these bright spots.
They are evidently small spots very much thicker — apparently many
times thicker — than the part of the film out of which they are formed.
Now if the formation of the black spots were due to a simple ex-
tension of the film, it is evident that no such appearance would
be presented. The thickening of the edge of the film cannot be
accounted for by contraction. For an extension of the upper portion
of the film and contraction of the lower and thicker portion, with
descent of the intervening portions, would be far less resisted by
viscosity, and far more favored by gravity than such extensions and
contractions as would produce the appearances described. But the
rapid formation of a thin spot by an internal current would cause
an accumulation at the edge of the spot of the material forming
the interior of the film, and necessitate a thickening of the film in
that place.
That which is most difficult to account for in the formation of
the black spots is the arrest of the process by which the film grows
thinner. It seems most natural to account for this, if possible, by
passive resistance to motion due to a very viscous or gelatinous
condition of the film. For it does not seem likely that the film,
after becoming unstable by the flux of matter from its interior, would
become stable (without the support of such resistance) by a continu-
ance of the same process. On the other hand, gelatinous properties
are very marked in soap-water which contains somewhat more soap
than is best for the formation of films, and it is entirely natural
that, even when such properties are wanting in the interior of a
mass or thick film of a liquid, they may still exist in the immediate
vicinity of the surface (where we know that the soap or some of
its components exists in excess), or throughout a film which is so
thin that the interior has ceased to have the properties of matter
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 313
in mass.* But these considerations do not amount to any a priori
probability of an arrest of the tendency toward an internal current
between adjacent elements of a black spot which may differ slightly
in thickness, in time to prevent rupture of the film. For, in a thick
film, the increase of the tension with the extension, which is necessary
for its stability with respect to extension, is connected with an excess
of the soap (or of some of its components) at the surface as compared
with the interior of the film. With respect to the black spots,
although the interior has ceased to have the properties of matter in
mass, and any quantitative determinations derived from the surfaces
of a mass of the liquid will not be applicable, it is natural to account
for the stability with reference to extension by supposing that the
same general difference of composition still exists. If therefore we
account for the arrest of internal currents by the increasing density
of soap or some of its components in the interior of the film, we
must still suppose that the characteristic difference of composition
in the interior and surface of the film has not been obliterated.
The preceding discussion relates to liquid films between masses of
gas. Similar considerations will apply to liquid films between other
liquids or between a liquid and a gas, and to films of gas between
masses of liquid. The latter may be formed by gently depositing a
liquid drop upon the surface of a mass of the same or a different
liquid. This may be done (with suitable liquids) so that the con-
tinuity of the air separating the liquid drop and mass is not broken,
but a film of air is formed, which, if the liquids are similar, is a
counterpart of the liquid film which is formed by a bubble of air
rising to the top of a mass of the liquid. (If the bubble has the
same volume as the drop, the films will have precisely the same
form, as well as the rest of the surfaces which bound the bubble
and the drop.) Sometimes, when the weight and momentum of
the drop carry it through the surface of the mass on which it falls,
it appears surrounded by a complete spherical film of air, which is
the counterpart on a small scale of a soap-bubble hovering in air.t
Since, however, the substance to which the necessary differences of
* The experiments of M. Plateau (chapter VII of the work already cited) show that
this is the case to a very remarkable degree with respect to a solution of saponine.
With respect to soap-water, however, they do not indicate any greater superficial
viscosity than belongs to pure water. But the resistance to an internal current, such
as we are considering, is not necessarily measured by the resistance to such motions
as those of the experiments referred to.
t These spherical air-films are easily formed in soap-water. They are distinguish-
able from ordinary air-bubbles by their general behavior and by their appearance.
The tv/o concentric spherical surfaces are distinctly seen, the diameter of one appearing
to be about three-quarters as large as that of the other. This is of course an optical
illusion, depending upon the index of refraction of the liquid.
314 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
tension in the film are mainly due is a component of the liquid
masses on each side of the air film, the necessary differences of the
potential of this substance cannot be permanently maintained, and
these films have little persistence compared with films of soap-water
in air. In this respect, the case of these air-films is analogous to
that of liquid films in an atmosphere containing substances by which
their tension is greatly reduced. Compare pages 310, 311.
Surfaces of Discontinuity between Solids and Fluids.
We have hitherto treated of surfaces of discontinuity on the
supposition that the contiguous masses are fluid. This is by far the
most simple case for any rigorous treatment, since the masses are
necessarily isotropic both in nature and in their state of strain. In
this case, moreover, the mobility of the masses allows a satisfactory
experimental verification of the mechanical conditions of equilibrium.
On the other hand, the rigidity of solids is in general so great, that
any tendency of the surfaces of discontinuity to variation in area or
form may be neglected in comparison with the forces which are
produced in the interior of the solids by any sensible strains, so
that it is not generally necessary to take account of the surfaces of
discontinuity in determining the state of strain of solid masses. But
we must take account of the nature of the surfaces of discontinuity
between solids and fluids with reference to the tendency toward soli-
dification or dissolution at such surfaces, and also with reference to
the tendencies of different fluids to spread over the surfaces of solids.
Let us therefore consider a surface of discontinuity between a fluid
and a solid, the latter being either isotropic or of a continuous crystal-
line structure, and subject to any kind of stress compatible with a
state of mechanical equilibrium with the fluid. We shall not exclude
the case in which substances foreign to the contiguous masses are
present in small quantities at the surface of discontinuity, but we
shall suppose that the nature of this surface (i.e., of the non-homo-
geneous film between the approximately homogeneous masses) is
entirely determined by the nature and state of the masses which it
separates, and the quantities of the foreign substances which may be
present. The notions of the dividing surface, and of the superficial
densities of energy, entropy, and the several components, which we
have used with respect to surfaces of discontinuity between fluids
(see pages 219 and 224), will evidently apply without modification to
the present case. We shall use the suffix l with reference to the
substance of the solid, and shall suppose the dividing surface to be
determined so as to make the superficial density of this substance
vanish. The superficial densities of energy, of entropy, and of the
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 315
other component substances may then be denoted by our usual
symbols (see page 235),
€s(D> ^s(i)> r2(ij, r3(1), etc.
Let the quantity or be defined by the equation
<r = e8(D ~ ^s(i) — faTw) — /x3r3(D — etc., (659)
in which t denotes the temperature, and //2, yu8, etc. the potentials
for the substances specified at the surface of discontinuity.
As in the case of two fluid masses (see page 257), we may regard
a- as expressing the work spent in forming a unit of the surface of
discontinuity — under certain conditions, which we need not here
specify — but it cannot properly be regarded as expressing the tension
of the surface. The latter quantity depends upon the work spent in
stretching the surface, while the quantity or depends upon the work
spent in forming the surface. With respect to perfectly fluid masses,
these processes are not distinguishable, unless the surface of discon-
tinuity has components which are not found in the contiguous masses,
and even in this case (since the surface must be supposed to be formed
out of matter supplied at the same potentials which belong to the
matter in the surface) the work spent in increasing the surface
infinitesimally by stretching is identical with that which must be
spent in forming an equal infinitesimal amount of new surface. But
when one of the masses is solid, and its states of strain are to be
distinguished, there is no such equivalence between the stretching of
the surface and the forming of new surface.*
* This will appear more distinctly if we consider a particular case. Let us consider
a thin plane sheet of a crystal in a vacuum (which may be regarded as a limiting case
of a very attenuated fluid), and let us suppose that the two surfaces of the sheet are
alike. By applying the proper forces to the edges of the sheet, we can make all stress
vanish in its interior. The tensions of the two surfaces are in equilibrium with these
forces, and are measured by them. But the tensions of the surfaces, thus determined,
may evidently have different values in different directions, and are entirely different
from the quantity which we denote by <r, which represents the work required to form
a unit of the surface by any reversible process, and is not connected with any idea of
direction.
In certain cases, however, it appears probable that the values of a and of the
superficial tension will not greatly differ. This is especially true of the numerous
bodies which, although generally (and for many purposes properly) regarded as solids,
are really very viscous fluids. Even when a body exhibits no fluid properties at its
actual temperature, if its surface has been formed at a higher temperature, at which
the body was fluid, and the change from the fluid to the solid state has been by
insensible gradations, we may suppose that the value of <r coincided with the superficial
tension until the body was decidedly solid, and that they will only differ so far as they
may be differently affected by subsequent variations of temperature and of the stresses
applied to the solid. Moreover, when an amorphous solid is in a state of equilibrium
with a solvent, although it may have no fluid properties in its interior, it seems not
improbable that the particles at its surface, which have a greater degree of mobility,
may so arrange themselves that the value of <r will coincide with the superficial tension,
as in the case of fluids.
316 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
With these preliminary notions, we now proceed to discuss the
condition of equilibrium which relates to the dissolving of a solid at
the surface where it meets a fluid, when the thermal and mechanical
conditions of equilibrium are satisfied. It will be necessary for us to
consider the case of isotropic and of crystallized bodies separately,
since in the former the value of tr is independent of the direction of
the surface, except so far as it may be influenced by the state of strain
of the solid, while in the latter the value of or varies greatly with the
direction of the surface with respect to the axes of crystallization, and
in such a manner as to have a large number of sharply defined
minima.* This may be inferred from the phenomena which crystal-
line bodies present, as will appear more distinctly in the following
discussion. Accordingly, while a variation in the direction of an
element of the surface may be neglected (with respect to its effect on
the value of <r) in the case of isotropic solids, it is quite otherwise
with crystals. Also, while the surfaces of equilibrium between fluids
and soluble isotropic solids are without discontinuities of direction,
being in general curved, a crystal in a state of equilibrium with a
fluid in which it can dissolve is bounded in general by a broken
surface consisting of sensibly plane portions.
For isotropic solids, the conditions of equilibrium may be deduced
as follows. If we suppose that the solid is unchanged, except that an
infinitesimal portion is dissolved at the surface where it meets the
fluid, and that the fluid is considerable in quantity and remains
homogeneous, the increment of energy in the vicinity of the surface
will be represented by the expression
/[ev'-ev"+(Cl + c2)e8(1)] SNDs
where Ds denotes an element of the surface, SN the variation in its
position (measured normally, and regarded as negative when the solid
is dissolved), cx and c2 its principal curvatures (positive when their
centers lie on the same side as the solid), es(1) the surface-density of
energy, ev' and ev" the volume-densities of energy in the solid and
fluid respectively, and the sign of integration relates to the elements
Ds. In like manner, the increments of entropy and of the quantities
of the several components in the vicinity of the surface will be
r' - >/v" + (c, 4- c,)fc(1)] SNDs,
etc.
The entropy and the matter of different kinds representd by these
* The differential coefficients of <r with respect to the direction-cosines of the surface
appear to be discontinuous functions of the latter quantities.
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 317
expressions we may suppose to be derived from the fluid mass.
These expressions, therefore, with a change of sign, will represent
the increments of entropy and of the quantities of the components
in the whole space occupied by the fluid except that which is
immediately contiguous to the solid. Since this space may be
regarded as constant, the increment of energy in this space may be
obtained (according to equation (12)) by multiplying the above
expression relating to entropy by —t, and those relating to the
components by — /*/', — yw2, etc.,* and taking the sum. If to this
we add the above expression for the increment of energy near the
surface, we obtain the increment of energy for the whole system.
Now by (93) we have
p" = — €y" + ^y" ~f" Ml Vl ~J~ At2<y2/' ~t~ 6^C*
By this equation and (659), our expression for the total increment of
energy in the system may be reduced to the form
f[ev' - tnv - A^V/ +p" + (cx + c2)<r] SNDa. (660)
In order that this shall vanish for any values of SN, it is necessary
that the coefficient of 8NDs shall vanish. This gives for the con-
dition of equilibrium
^ Yi
This equation is identical with (387), with the exception of the term
containing o-, which vanishes when the surface is plane.t
We may also observe that when the solid has no stresses except an
isotropic pressure, if the quantity represented by a- is equal to the true
tension of the surface, p" ' + (c1 + c^)ar will represent the pressure in
the interior of the solid, and the second member of the equation will
represent (see equation (93)) the value of the potential in the solid
for the substance of which it consists. In this case, therefore, the
equation reduces to
that is, it expresses the equality of the potentials for the substance of
*The potential fj^" is marked by double accents in order to indicate that its value
is to be determined in the fluid mass, and to distinguish it from the potential ft/
relating to the solid mass (when this is in a state of isotropic stress), which, as we
shall see, may not always have the same value. The other potentials /-Uj, etc., have
the same values as in (659), and consist of two classes, one of which relates to sub-
stances which are components of the fluid mass (these might be marked by the double
accents), and the other relates to substances found only at the surface of discontinuity.
The expressions to be multiplied by the potentials of this latter class all have the
value zero.
fin equation (387), the density of the solid is denoted by F, which is therefore
equivalent to ?/ in (661 ).
318 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
the solid in the two masses — the same condition which would subsist
if both masses were fluid.
Moreover, the compressibility of all solids is so small that, although
or may not represent the true tension of the surface, nor p" + (c^c^cr
the true pressure in the solid when its stresses are isotropic, the quan-
tities ev' and jyv' if calculated for the pressure ^//+(c1+c2)o- with
the actual temperature will have sensibly the same values as if calcu-
lated for the true pressure of the solid. Hence, the second member
of equation (661), when the stresses of the solid are sensibly isotropic,
is sensibly equal to the potential of the same body at the same tem-
perature but with the pressure fi'+^+c^a; and the condition of
equilibrium with respect to dissolving for a solid of isotropic stresses
may be expressed with sufficient accuracy by saying that the potential
for the substance of the solid in the fluid must have this value. In
like manner, when the solid is not in a state of isotropic stress, the
difference of the two pressures in question will not sensibly affect
the values of ev' and jjv', and the value of the second member of the
equation may be calculated as if p" + (c^c^cr represented the true
pressure in the solid in the direction of the normal to the surface.
Therefore, if we had taken for granted that the quantity or represents
the tension of a surface between a solid and a fluid, as it does when
both masses are fluid, this assumption would not have led us into any
practical error in determining the value of the potential ///' which is
necessary for equilibrium. On the other hand, if in the case of any
amorphous body the value of or differs notably from the true surface-
tension, the latter quantity substituted for <j in (661) will make the
second member of the equation equal to the true value of /*/, when
the stresses are isotropic, but this will not be equal to the value of /x/'
in case of equilibrium, unless ^-f c2 = 0.
When the stresses in the solid are not isotropic, equation (661)
may be regarded as expressing the condition of equilibrium with
respect to the dissolving of the solid, and is to be distinguished from
the condition of equilibrium with respect to an increase of solid
matter, since the new matter would doubtless be deposited in a state
of isotropic stress. (The case would of course be different with
crystalline bodies, which are not considered here.) The value of
/*/' necessary for equilibrium with respect to the formation of new
matter is a little less than that necessary for equilibrium with respect
to the dissolving of the solid. In regard to the actual behavior of
the solid and fluid, all that the theory enables us to predict with
certainty is that the solid will not dissolve if the value of the poten-
tial [if is greater than that given by the equation for the solid with
its distorting stresses, and that new matter will not be formed if the
value of PI is less than the same equation would give for the case of
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 319
the solid with isotropic stresses.* It seems probable, however, that
if the fluid in contact with the solid is not renewed, the system will
generally find a state of equilibrium in which the outermost portion
of the solid will be in a state of isotropic stress. If at first the solid
should dissolve, this would supersaturate the fluid, perhaps until a
state is reached satisfying the condition of equilibrium with the
stressed solid, and then, if not before, a deposition of solid matter in a
state of isotropic stress would be likely to commence and go on until
the fluid is reduced to a state of equilibrium with this new solid
matter.
The action of gravity will not affect the nature of the condition of
equilibrium for any single point at which the fluid meets the solid, but
it will cause the values of p" and fa" in (661) to vary according to
the laws expressed by (612) and (617). If we suppose that the outer
part of the solid is in a state of isotropic stress, which is the most
important case, since it is the only one in which the equilibrium is in
every sense stable, we have seen that the condition (661) is at least
sensibly equivalent to this : — that the potential for the substance of
the solid which would belong to the solid mass at the temperature t
and the pressure p"+(c1H-c2)0" must be equal to fa". Or, if we denote
by (p') the pressure belonging to solid with the temperature t and the
potential equal to fa", the condition may be expressed in the form
(/)=/' +(Cl + C2)o-. (662)
Now if we write y" for the total density of the fluid, we have by (612)
By (98)
and by (617) dfa" = —gdz\
whence d(p') — — g y^dz.
Accordingly we have
and
z being measured from the horizontal plane for which (p')=p".
Substituting this value in (662), we obtain
*The possibility that the new solid matter might differ in composition from the
original solid is here left out of account. This point has been discussed on pages
79-82, but without reference to the state of strain of the solid or the influence of
the curvature of the surface of discontinuity. The statement made above may be
generalized so as to hold true of the formation of new solid matter of any kind on
the surface as follows : — that new solid matter of any kind will not be formed upon
the surface (with more than insensible thickness), if the second member of (661) cal-
culated for such new matter is greater than the potential in the fluid for such matter.
320 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
precisely as if both masses were fluid, and a- denoted the tension
of their common surface, and (pf) the true pressure in the mass
specified. (Compare (619).)
The obstacles to an exact experimental realization of these relations
are very great, principally from the want of absolute uniformity in
the internal structure of amorphous solids, and on account of the
passive resistances to the processes which are necessary to bring
about a state satisfying the conditions of theoretical equilibrium,
but it may be easy to verify the general tendency toward diminution
of surface, which is implied in the foregoing equations.*
Let us apply the same method to the case in which the solid
is a crystal. The surface between the solid and fluid will now
consist of plane portions, the directions of which may be regarded
as invariable. If the crystal grows on one side a distance SN,
without other change, the increment of energy in the vicinity of
the surface will be
(ev' - ev'> 8N+ If(em' I' cosec o>' - es(1) I' cot co')SN,
*It seems probable that a tendency of this kind plays an important part in some
of the phenomena which have been observed with respect to the freezing together
of pieces of ice. (See especially Professor Faraday's "Note on Regelation" in the
Proceedings of the Royal Society, vol. x, p. 440 ; or in the Philosophical Magazine,
4th ser., vol. xxi, p. 146.) Although this is a body of crystalline structure, and
the action which takes place is doubtless influenced to a certain extent by the
directions of the axes of crystallization, yet since the phenomena have not been
observed to depend upon the orientation of the pieces of ice we may conclude that
the effect, so far as its general character is concerned, is such as might take place
with an isotropic body. In other words, for the purposes of a general explanation
of the phenomena we may neglect the differences in the values of <7IW (the suffixes
are used to indicate that the symbol relates to the surface between ice and water)
for different orientations of the axes of crystallization, and also neglect the influence
of the surface of discontinuity with respect to crystalline structure, which must be
formed by the freezing together of the two masses of ice when the axes of crystal-
lization in the two masses are not similarly directed. In reality, this surface — or
the necessity of the formation of such a surface if the pieces of ice freeze together-
must exert an influence adverse to their union, measured by a quantity <rn, which is
determined for this surface by the same principles as when one of two contiguous
masses is fluid, and varies with the orientations of the two systems of crystallographic
axes relatively to each other and to the surface. But under the circumstances of
the experiment, since we may neglect the possibility of the two systems of axes
having precisely the same directions, this influence is probably of a tolerably constant
character, and is evidently not sufficient to alter the general nature of the result.
In order wholly to prevent the tendency of pieces of ice to freeze together, when
meeting in water with curved surfaces and without pressure, it would be necessary
that <rn^2oriw, except so far as the case is modified by passive resistances to change,
and by the inequality in the values of <TH and <riw for different directions of the axes
of crystallization.
It will be observed that this view of the phenomena is in harmony with the
opinion of Professor Faraday. With respect to the union of pieces of ice as an
indirect consequence of pressure, see page 198 of volume xi of the Proceedings of
the Royal Society; or the Philosophical Magazine, 4th ser., vol. xxiii, p. 407.
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 321
where ev' and ev" denote the volume-densities of energy in the
crystal and fluid respectively, s the area of the side on which the
crystal grows, es(1) the surface-density of energy on that side, eB(1)'
the surface-density of energy on an adjacent side, «' the external
angle of these two sides, I' their common edge, and the symbol 2'
a summation with respect to the different sides adjacent to the
first. The increments of entropy and of the quantities of the several
components will be represented by analogous formulae, and if we
deduce as on pages 316, 317 the expression for the increase of
energy in the whole system due to the growth of the crystal
without change of the total entropy or volume, and set this expres-
sion equal to zero, we shall obtain for the condition of equilibrium
(ev' _ t^ - yu/'y/ +jp")8 SN+ 2'(<rT cosec o>' - d! cot w)6N= 0, (664)
where cr and or' relate respectively to the same sides as es(1) and es(1)'
in the preceding formula. This gives
2'(o-
1
It will be observed that unless the side especially considered is
small or narrow, we may neglect the second fraction in this
equation, which will then give the same value of /*/' as equation
(387), or as equation (661) applied to a plane surface.
Since a similar equation must hold true with respect to every
other side of the crystal of which the equilibrium is not affected
by meeting some other body, the condition of equilibrium for the
crystalline form (when unaffected by gravity) is that the expression
2'(o-T cosec ft/ — o-l' cot ft/) /™*\
- - - (666)
shall have the same value for each side of the crystal. (By the
value of this expression for any side of the crystal is meant its
value when a- and s are determined by that side and the other
quantities by the surrounding sides in succession in connection with
the first side.) This condition will not be affected by a change in
the size of a crystal while its proportions remain the same. But
the tendencies of similar crystals toward the form required by this
condition, as measured by the inequalities in the composition or the
temperature of the surrounding fluid which would counterbalance
them, will be inversely as the linear dimensions of the crystals, as
appears from the preceding equation.
If we write v for the volume of a crystal, and S(o-s) for the sum
of the areas of all its sides multiplied each by the corresponding
value of o-, the numerator and denominator of the fraction (666),
multiplied each by 8N, may be represented by <$2(<rs) and Sv
G.I. x
322 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
respectively. The value of the fraction is therefore equal to that
of the differential coefficient
dl,(a-s)
dv
as determined by the displacement of a particular side while the
other sides are fixed. The condition of equilibrium for the form
of a crystal (when the influence of gravity may be neglected) is
that the value of this differential coefficient must be independent
of the particular side which is supposed to be displaced. For a
constant volume of the crystal, 2(o-s) has therefore a minimum value
when the condition of equilibrium is satisfied, as may easily be
proved more directly.
When there are no foreign substances at the surfaces of the
crystal, and the surrounding fluid is indefinitely extended, the
quantity 2(o-s) represents the work required to form the surfaces
of the crystal, and the coefficient of sSN in (664) with its sign
reversed represents the work gained in forming a mass of volume
unity like the crystal but regarded as without surfaces. We may
denote the work required to form the crystal by
WB-WV,
Ws denoting the work required to form the surfaces {i.e., Z(o-s)},
and W^ the work gained in forming the mass as distinguished from
the surfaces. Equation (664) may then be written
-($Fv + Z(er<te) = 0. (667)
Now (664) would evidently continue to hold true if the crystal
were diminished in size, remaining similar to itself in form and
in nature, if the values of a- in all the sides were supposed to
diminish in the same ratio as the linear dimensions of the crystal.
The variation of Ws would then be determined by the relation
d W8 = d2(<rs) = f 2(<r ds), '
and that of Fv by (667). Hence,
and, since WB and TFV vanish together,
8 V 3 8 2 V' \ /
— the same relation which we have before seen to subsist with
respect to a spherical mass of fluid as well as in other cases. (See
pages 257, 261, 298.)
The equilibrium of the crystal is unstable with respect to variations
in size when the surrounding fluid is indefinitely extended, but it
may be made stable by limiting the quantity of the fluid.
EQUILIBEIUM OF HETEROGENEOUS SUBSTANCES. 323
To take account of the influence of gravity, we must give to fi^f
and p" in (665) their average values in the side considered. These
coincide (when the fluid is in a state of internal equilibrium) with
their values at the center of gravity of the side. The values of
y\t GV> *lv may b6 regarded as constant, so far as the influence of
gravity is concerned. Now since by (612) and (617)
and
we have
Comparing (664), we see that the upper or the lower faces of the
crystal will have the greater tendency to grow (other things being
equal), according as the crystal is lighter or heavier than the fluid.
When the densities of the two masses are equal, the effect of gravity
on the form of the crystal may be neglected.
In the preceding paragraph the fluid is regarded as in a state
of internal equilibrium. If we suppose the composition and tem-
perature of the fluid to be uniform, the condition which will make
the effect of gravity vanish will be that
dz
when the value of the differential coefficient is determined in
accordance with this supposition. This condition reduces to
yx"
which, by equation (92), is equivalent to
=A- (669)
The tendency of a crystal to grow will be greater in the upper
or lower parts of the fluid, according as the growth of a crystal
at constant temperature and pressure will produce expansion or
contraction.
Again, we may suppose the composition of the fluid and its entropy
per unit of mass to be uniform. The temperature will then vary with
the pressure, that is, with z. We may also suppose the temperature
of different crystals or different parts of the same crystal to be deter-
mined by the fluid in contact with them. These conditions express a
state which may perhaps be realized when the fluid is gently stirred.
Owing to the differences of temperature we cannot regard ev' and rjv'
*A suffixed m is used to represent all the symbols m^, m%, etc., except such as
may occur in the differential coefficient.
324 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
in (664) as constant, but we may regard their variations as subject to
the relation dev' = t dqv'. Therefore, if we make q? = 0 for the mean
temperature of the fluid (which involves no real loss of generality),
we may treat ev'— fo/v' as constant. We shall then have for the con-
dition that the effect of gravity shall vanish
dz
which signifies in the present case that
=1
m y/'
or, by (90),
=-• (670)
Since the entropy of the crystal is zero, this equation expresses
that the dissolving of a small crystal in a considerable quantity of
the fluid will produce neither expansion nor contraction, when the
pressure is maintained constant and no heat is supplied or taken
away.
The manner in which crystals actually grow or dissolve is often
principally determined by other differences of phase in the surrounding
fluid than those which have been considered in the preceding para-
graph. This is especially the case when the crystal is growing or
dissolving rapidly. When the great mass of the fluid is considerably
supersaturated, the action of the crystal keeps the part immediately
contiguous to it nearer the state of exact saturation. The farthest
projecting parts of the crystal will therefore be most exposed to the
action of the supersaturated fluid, and will grow most rapidly. The
same parts of a crystal will dissolve most rapidly in a fluid con-
siderably below saturation.*
But even when the fluid is supersaturated only so much as is
necessary in order that the crystal shall grow at all, it is not to be
expected that the form in which Z(crs) has a minimum value (or
such a modification of that form as may be due to gravity or to the
influence of the body supporting the crystal) will always be the
ultimate result. For we cannot imagine a body of the internal
structure and external form of a crystal to grow or dissolve by an
entirely continuous process, or by a process in the same sense con-
tinuous as condensation or evaporation between a liquid and gas, or
the corresponding processes between an amorphous solid and a fluid.
The process is rather to be regarded as periodic, and the formula (664)
*SeeO. Lehmann, "Ueber das Wachsthum der Krystalle," Zeitschrift fur Krystal-
lographie und Mineralogie, Bd. i, S. 453 ; or the review of the paper in Wiedemann's
BeiMdtter, Bd. ii, S. 1.
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 325
cannot properly represent the true value of the quantities intended
unless SN is equal to the distance between two successive layers of
molecules in the crystal, or a multiple of that distance. Since this
can hardly be treated as an infinitesimal, we can only conclude with
certainty that sensible changes cannot take place for which the
expression (664) would have a positive value.*
* That it is necessary that certain relations shall be precisely satisfied in order that
equilibrium may subsist between a liquid and gas with respect to evaporation, is
explained (see Clausius, "Ueber die Art der Bewegung, welche wir Warme nennen,"
Pogg. Ann., Bd. o, S. 353 ; or Abhand. iiber die median. Warmetheorie, XIV) by suppos-
ing that a passage of individual molecules from the one mass to the other is continually
taking place, so that the slightest circumstance may give the preponderance to the
passage of matter in either direction. The same supposition may be applied, at least
in many cases, to the equilibrium between amorphous solids and fluids. Also in the
case of crystals in equilibrium with fluids, there may be a passage of individual mole-
cules from one mass to the other, so as to cause insensible fluctuations in the mass of
the solid. If these fluctuations are such as to cause the occasional deposit or removal
of a whole layer of particles, the least cause would be sufficient to make the probability
of one kind of change prevail over that of the other, and it would be necessary for
equilibrium that the theoretical conditions deduced above should be precisely satisfied.
But this supposition seems quite improbable, except with respect to a very small side.
The following view of the molecular state of a crystal when in equilibrium with
respect to growth or dissolution appears as probable as any. Since the molecules at
the corners and edges of a perfect crystal would be less firmly held in their places
than those in the middle of a side, we may suppose that when the condition of
theoretical equilibrium (665) is satisfied several of the outermost layers of molecules
on each side of the crystal are incomplete toward the edges. The boundaries of these
imperfect layers probably fluctuate, as individual molecules attach themselves to the
crystal or detach themselves, but not so that a layer is entirely removed (on any side
of considerable size), to be restored again simply by the irregularities of the motions
of the individual molecules. Single molecules or small groups of molecules may
indeed attach themselves to the side of the crystal but they will speedily be dislodged,
and if any molecules are thrown out from the middle of a surface, these deficiencies
will also soon be made good ; nor will the frequency of these occurrences be such as
greatly to affect the general smoothness of the surfaces, except near the edges where
the surfaces fall off somewhat, as before described. Now a continued growth on any
side of a crystal is impossible unless new layers can be formed. This will require a
value of fa" which may exceed that given by equation (665) by a finite quantity.
Since the difficulty in the formation of a new layer is at or near the commencement
of the formation, the necessary value of p." may be independent of the area of the
side, except when the side is very small. The value of fa" which is necessary for the
growth of the crystal will however be different for different kinds of surfaces, and
probably will generally be greatest for the surfaces for which a- is least.
On the whole, it seems not improbable that the form of very minute crystals in
equilibrium with solvents is principally determined by equation (665), (i.e., by the
condition that 2(<r«) shall be a minimum for the volume of the crystal except so far
as the case is modified by gravity or the contact of other bodies), but as they grow
larger (in a solvent no more supersaturated than is necessary to make them grow at
all), the deposition of new matter on the different surfaces will be determined more by
the nature (orientation) of the surfaces and less by their size and relations to the
surrounding surfaces. As a final result, a large crystal, thus formed, will generally
be bounded by those surfaces alone on which the deposit of new matter takes place
least readily, with small, perhaps insensible truncations. If one kind of surfaces
326 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
Let us now examine the special condition of equilibrium which
relates to a line at which three different masses meet, when one or
more of these masses is solid. If we apply the method of pages 316,
317 to a system containing such a line, it is evident that we shall
obtain in the expression corresponding to (660), beside the integral
relating to the surfaces, a term of the form
to be interpreted as the similar term in (611), except so far as the
definition of cr has been modified in its extension to solid masses. In
order that this term shall be incapable of a negative value it is
necessary that at every point of the line
2(<r£T)^0 (671)
for any possible displacement of the line. Those displacements are to
be regarded as possible which are not prevented by the solidity of the
masses, when the interior of every solid mass is regarded as incapable
of motion. At the surfaces between solid and fluid masses, the pro-
cesses of solidification and dissolution will be possible in some cases,
and impossible in others.
The simplest case is when two masses are fluid and the third is
solid and insoluble. Let us denote the solid by S, the fluids by
A and B, and the angles filled by these fluids by a and /3 respec-
tively. If the surface of the solid is continuous at the line where it
meets the two fluids, the condition of equilibrium reduces to
<rAB cos a = <TBS ~ ^AS • (672)
If the line where these masses meet is at an edge of the solid, the
condition of equilibrium is that
OAB cos a ^ o-BS - <rA8,\
and <7AB cos /3 ^ <rA8 - (rB8 ;/
which reduces to the preceding when a + /3 = 7r. Since the displace-
ment of the line can take place by a purely mechanical process, this
satisfying this condition cannot form a closed figure, the crystal will be bounded by
two or three kinds of surfaces determined by the same condition. The kinds of
surface thus determined will probably generally be those for which <r has the least
values. But the relative development of the different kinds of sides, even if unmodi-
fied by gravity or the contact of other bodies, will not be such as to make S(<rs) a
minimum. The growth of the crystal will finally be confined to sides of a single kind.
It does not appear that any part of the operation of removing a layer of molecules
presents any especial difficulty so marked as that of commencing a new layer ; yet
the values of fj^" which will »just allow the different stages of the process to go on
must be slightly different, and therefore, for the continued dissolving of the crystal
the value of /*/' must be less (by a finite quantity) than that given by equation (665).
It seems probable that this would be especially true of those sides for which cr has
the least values. The effect of dissolving a crystal (even when it is done as slowly
as possible) is therefore to produce a form which probably differs from that of
theoretical equilibrium in a direction opposite to that of a growing crystal.
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 327
condition is capable of a more satisfactory experimental verification
than those conditions which relate to processes of solidification and
dissolution. Yet the fractional resistance to a displacement of the line
is enormously greater than in the case of three fluids, since the
relative displacements of contiguous portions of matter are enormously
greater. Moreover, foreign substances adhering to the solid are not
easily displaced, and cannot be distributed by extensions and con-
tractions of the surface of discontinuity, as in the case of fluid masses.
Hence, the distribution of such substances is arbitrary to a greater
extent than in the case of fluid masses (in which a single foreign
substance in any surface of discontinuity is uniformly distributed,
and a greater number are at least so distributed as to make the
tension of the surface uniform), and the presence of these substances
will modify the conditions of equilibrium in a more irregular manner.
If one or more of three surfaces of discontinuity which meet in a
line divides an amorphous solid from a fluid in which it is soluble,
such a surface is to be regarded as movable, and the particular con-
ditions involved in (671) will be accordingly modified. If the soluble
solid is a crystal, the case will properly be treated by the method
used on pages 320, 321. The condition of equilibrium relating to the
line will not in this case be entirely separable from those relating to
the adjacent surfaces, since a displacement of the line will involve a
displacement of the whole side of the crystal which is terminated at
this line. But the expression for the total increment of energy in the
system due to any internal changes not involving any variation in
the total entropy or volume will consist of two parts, of which one
relates to the properties of the masses of the system, and the other
may be expressed in the form
the summation relating to all the surfaces of discontinuity. This
indicates the same tendency towards changes diminishing the value
of Z(o-s), which appears in other cases.*
* The freezing together of wool and ice may be mentioned here. The fact that a fiber
of wool which remains in contact with a block of ice under water will become attached
to it seems to be strictly analogous to the fact that if a solid body be brought into such
a position that it just touches the free surface of water, the water will generally rise up
about the point of contact so as to touch the solid over a surface of some extent. The
condition of the latter phenomenon is
where the suffixes 8, A, and w refer to the solid, to air, and to water, respectively. In
like manner, the condition for the freezing of the ice to the wool, if we neglect the
seolotropic properties of the ice, is
where the suffixes e> w> and i relate to wool, to water, and to ice, respectively. See
Proc. Roy. Soc., vol. x, p. 447; or Phil. Mag., 4th ser., vol. xxi, p. 151.
328 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
General Relations. — For any constant state of strain of the surface
of the solid we may write
dem = tdriS[l)+fadri(l}+fJi3dr8W+ete., (674)
since this relation is implied in the definition of the quantities involved.
From this and (659) we obtain
da-= ~-ijB(i)dt-~'r*(i)dt*2-~r3(l)d[i3- etc., (675)
which is subject, in strictness, to the same limitation — that the state
of strain of the surface of the solid remains the same. But this
limitation may in most cases be neglected. (If the quantity <r repre-
sented the true tension of the surface, as in the case of a surface
between fluids, the limitation would be wholly unnecessary.)
Another method and notation. — We have so far supposed that
we have to do with a non-homogeneous film of matter between
two homogeneous (or very nearly homogeneous) masses, and that
the nature and state of this film is in all respects determined by the
nature and state of these masses together with the quantities of the
foreign substances which may be present in the film. (See page 314.)
Problems relating to processes of solidification and dissolution seem
hardly capable of a satisfactory solution, except on this supposition,
which appears in general allowable with respect to the surfaces
produced by these processes. But in considering the equilibrium of
fluids at the surface of an unchangeable solid, such a limitation is
neither necessary nor convenient. The following method of treating
the subject will be found more simple and at the same time more
general.
Let us suppose the superficial density of energy to be determined
by the excess of energy in the vicinity of the surface over that which
would belong to the solid, if (with the same temperature and state
of strain) it were bounded by a vacuum in place of the fluid, and to
the fluid, if it extended with a uniform volume-density of energy just
up to the surface of the solid, or, if in any case this does not suffi-
ciently define a surface, to a surface determined in some definite way
by the exterior particles of the solid. Let us use the symbol (es) to
denote the superficial energy thus defined. Let us suppose a superficial
density of entropy to be determined in a manner entirely analogous,
and be denoted by (?/s). In like manner also, for all the components
of the fluid, and for all foreign fluid substances which may be present
at the surface, let the superficial densities be determined, and denoted
by (F2), (F3), etc. These superficial densities of the fluid components
relate solely to the matter which is fluid or movable. All matter
which is immovably attached to the solid mass is to be regarded as a
part of the same. Moreover, let y be defined by the equation
9 = («B) - *(*s) - ft(rs) - yU3(F3) - etc. (676)
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 329
These quantities will satisfy the following general relations : —
d(eB) = t d(riB) + fJL2 d(T2) + /*3 d(T8) + etc., (677)
* = - (n*)dt - (r2)^2 - (TJdpt = etc. (678)
In strictness, these relations are subject to the same limitation as
(674) and (675). But this limitation may generally be neglected.
In fact, the values of ?, (es), etc. must in general be much less affected
by variations in the state of strain of the surface of the solid than
those of or, es(1), etc.
The quantity 9 evidently represents the tendency to contraction in
that portion of the surface of the fluid which is in contact with the
solid. It may be called the superficial tension of the fluid in contact
with the solid. Its value may be either positive or negative.
It will be observed for the same solid surface and for the same
temperature but for different fluids the values of a- (in all cases to
which the definition of this quantity is applicable) will differ from
those of 9 by a constant, viz., the value of a- for the solid surface in
a vacuum.
For the condition of equilibrium of two different fluids at a line on
the surface of the solid, we may easily obtain
(7AB cos a = ?BS — ?AS , (679)
the suffixes, etc., being used as in (672), and the condition being
subject to the same modification when the fluids meet at an edge of
the solid.
It must also be regarded as a condition of theoretical equilibrium
at the line considered (subject, like (679), to limitation on account of
passive resistances to motion), that if there are any foreign substances
in the surfaces A-S and B-S, the potentials for these substances shall
have the same value on both sides of the line; or, if any such sub-
stance is found only on one side of the line, that the potential for
that substance must not have a less value on the other side ; and that
the potentials for the components of the mass A, for example, must
have the same values in the surface B-C as in the mass A, or, if they
are not actual components of the surface B-C, a value not less than
in A. Hence, we cannot determine the difference of the surface-
tensions of two fluids in contact with the same solid, by bringing
them together upon the surface of the solid, unless these conditions
are satisfied, as well as those which are necessary to prevent the
mixing of the fluid masses.
The investigation on pages 276-282 of the conditions of equilibrium
for a fluid system under the influence of gravity may easily be
extended to the case in which the system is bounded by or includes
solid masses, when these can be treated as rigid and incapable of
330 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
dissolution. The general condition of mechanical equilibrium would
be of the form
-fp SDv +fgy Sz Dv+fa- SDs +fgT Sz Da
+fg Sz Dm +/9 SDs +fg(T)te Ds = 0, (680)
where the first four integrals relate to the fluid masses and the
surfaces which divide them, and have the same signification as in
equation (606), the fifth integral relates to the movable solid masses,
and the sixth and seventh to the surfaces between the solids and
fluids, (F) denoting the sum of the quantities (r2), (F3), etc. It should
be observed that at the surface where a fluid meets a solid Sz and Sz,
which indicate respectively the displacements of the solid and the
fluid, may have different values, but the components of these dis-
placements which are normal to the surface must be equal.
From this equation, among other particular conditions of equili-
brium, we may derive the following : —
df=g(T)dz (681)
(compare (614)), which expresses the law governing the distribution
of a thin fluid film on the surface of a solid, when there are no passive
resistances to its motion.
By applying equation (680) to the case of a vertical cylindrical tube
containing two different fluids, we may easily obtain the well-known
theorem that the product of the perimeter of the internal surface by
the difference 9' — 9" of the superficial tensions of the upper and lower
fluids in contact with the tube is equal to the excess of weight of the
matter in the tube above that which would be there, if the boundary
between the fluids were in the horizontal plane at which their pres-
sures would be equal. In this theorem, we may either include or
exclude the weight of a film of fluid matter adhering to the tube.
The proposition is usually applied to the column of fluid in moss
between the horizontal plane for which p' =p" and the actual boundary
between the two fluids. The superficial tensions 9' and 9" are then to
be measured in the vicinity of this column. But we may also include
the weight of a film adhering to the internal surface of the tube.
For example, in the case of water in equilibrium with its own vapor
in a tube, the weight of all the water-substance in the tube above the
plane p'=p", diminished by that of the water- vapor which would fill
the same space, is equal to the perimeter multiplied by the difference
in the values of 9 at the top of the tube and at the plane p' =p". If
the height of the tube is infinite, the value of 9 at the top vanishes,
and the weight of the film of water adhering to the tube and of the
mass of liquid water above the plane p' =p" diminished by the weight
of vapor which would fill the same space is equal in numerical value
but of opposite sign to the product of the perimeter of the internal
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 331
surface of the tube multiplied by 9", the superficial tension of liquid
water in contact with the tube at the pressure at which the water
and its vapor would be in equilibrium at a plane surface. In this
sense, the total weight of water which can be supported by the tube
per unit of the perimeter of its surface is directly measured by the
value of — ? for water in contact with the tube.
Modification of the Conditions of Equilibrium by Electromotive
Force.— Theory of a Perfect Electro-Chemical Apparatus.
We know by experience that in certain fluids (electrolytic con-
ductors) there is a connection between the fluxes of the component
substances and that of electricity. The quantitative relation between
these fluxes may be expressed by an equation of the form
~ Dm. , Dm*. , Dm* Dm^
De = - -H -- -+etc. --- * — -—etc., (682)
«a «b «g ah
where De, Dm&, etc. denote the infinitesimal quantities of electricity
and of the components of the fluid which pass simultaneously through
any same surface, which may be either at rest or in motion, and
aa, «b> etc., ag, ah, etc. denote positive constants. We may evidently
regard Dma, Drn^, etc., Dmg, .Z)rah, etc. as independent of one another.
For, if they were not so, one or more could be expressed in terms of
the others, and we could reduce the equation to a shorter form in
which all the terms of this kind would be independent.
Since the motion of the fluid as a whole will not involve any
electrical current, the densities of the components specified by the
suffixes must satisfy the relation
(683)
«a «b «g «h
These densities, therefore, are not independently variable, like the
densities of the components which we have employed in other cases.
We may account for the relation (682) by supposing that electricity
(positive or negative) is inseparably attached to the different kinds of
molecules, so long as they remain in the interior of the fluid, in such a
way that the quantities aa, ab, etc. of the substances specified are each
charged with a unit of positive electricity, and the quantities ag, ah,
etc. of the substances specified by these suffixes are each charged with
a unit of negative electricity. The relation (683) is accounted for by
the fact that the constants aa, ag, etc. are so small that the electrical
charge of any sensible portion j£ the fluid varying sensibly from
the law expressed in (683) would be enormously great, so that
the formation of such a mass would be resisted by a very great
force.
332 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
It will be observed that the choice of the substances which we
regard as the components of the fluid is to some extent arbitrary, and
that the same physical relations may be expressed by different
equations of the form (682), in which the fluxes are expressed with
reference to different sets of components. If the components chosen
are such as represent what we believe to be the actual molecular
constitution of the fluid, those of which the fluxes appear in the
equation of the form (682) are called the ions, and the constants of
the equation are called their electro-chemical equivalents. For our
present purpose, which has nothing to do with any theories of mole-
cular constitution, we may choose such a set of components as may be
convenient, and call those ions, of which the fluxes appear in the
equation of the form (682), without farther limitation.
Now, since the fluxes of the independently variable components of
an electrolytic fluid do not necessitate any electrical currents, all the
conditions of equilibrium which relate to the movements of these
components will be the same as if the fluid were incapable of the
electrolytic process. Therefore all the conditions of equilibrium which
we have found without reference to electrical considerations, will
apply to an electrolytic fluid and its independently variable com-
ponents. But we have still to seek the remaining conditions of
equilibrium, which relate to the possibility of electrolytic conduction.
For simplicity, we shall suppose that the fluid is without internal
surfaces of discontinuity (and therefore homogeneous except so far as
it may be slightly affected by gravity), and that it meets metallic
conductors (electrodes) in different parts of its surface, being other-
wise bounded by non-conductors. The only electrical currents which
it is necessary to consider are those which enter the electrolyte at
one electrode and leave it at another.
If all the conditions of equilibrium are fulfilled in a given state of
the system, except those which relate to changes involving a flux of
electricity, and we imagine the state of the system to be varied by
the passage from one electrode to another of the quantity of electricity
Se accompanied by the quantity £ma of the component specified,
without any flux of the other components or any variation in the
total entropy, the total variation of energy in the system will be
represented by the expression
in which V, V" denote the electrical potentials in pieces of the same
kind of metal connected with the two electrodes, Y', Y", the gravita-
tional potentials at the two electrodes, and ///, JUL&", the intrinsic
potentials for the substance specified. The first term represents
the increment of the potential energy of electricity, the second the
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 333
increment of the intrinsic energy of the ponderable matter, and the
third the increment of the energy due to gravitation.* But by (682)
It is therefore necessary for equilibrium that
V"- F'+aa(yua"-//a'- Y"+ Y') = 0. (684)
To extend this relation to all the electrodes we may write
F' + a^'- Y> F"+a.OC- Y") = F" + aaOC'- Y'") = etc. (685)
For each of the other cations (specified by b etc.) there will be a
similar condition, and for each of the anions a condition of the form
V - ag(fjLe' - Y') = F" - ag(figf/ - Y") = V" - ag(,ug'" - Y"') = etc. (686)
When the effect of gravity may be neglected, and there are but two
electrodes, as in a galvanic or electrolytic cell, we have for any cation
V"-V =«.(/!.' -//."), (687)
and for any anion
V"-V' = aM'-tte'), (688)
where V" — V denotes the electromotive force of the combination.
That is:—
When all the conditions of equilibrium are fulfilled in a galvanic
or electrolytic cell, the electromotive force is equal to the difference
in the values of the potential for any ion or apparent ion at the
surfaces of the electrodes multiplied by the electro-chemical equivalent
of that ion, the greater potential of an anion being at the same
electrode as the greater electrical potential, and the reverse being
true of a cation.
Let us apply this principle to different cases.
(I.) If the ion is an independently variable component of an
electrode, or by itself constitutes an electrode, the potential for the
ion (in any case of equilibrium which does not depend upon passive
resistances to change) will have the same value within the electrode
as on its surface, and will be determined by the composition of
the electrode with its temperature and pressure. This might be
illustrated by a cell with electrodes of mercury containing certain
quantities of zinc in solution (or with one such electrode and the
other of pure zinc) and an electrolytic fluid containing a salt of
zinc, but not capable of dissolving the mercury.! We may regard
* It is here supposed that the gravitational potential may be regarded as constant for
each electrode. When this is not the case the expression may be applied to small parts
of the electrodes taken separately.
t If the electrolytic fluid dissolved the mercury as well as the zinc, equilibrium
could only subsist when the electromotive force is zero, and the composition of the
electrodes identical. For when the electrodes are formed of the two metals in
different proportions, that which has the greater potential for zinc will have the less
potential for mercury. (See equation (98).) This is inconsistent with equilibrium,
according to the principle mentioned above, if both metals can act as cations.
334 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
a cell in which hydrogen acts as an ion between electrodes of
palladium charged with hydrogen as another illustration of the same
principle, but the solidity of the electrodes and the consequent
resistance to the diffusion of the hydrogen within them (a process
which cannot be assisted by convective currents as in a liquid mass)
present considerable obstacles to the experimental verification of the
relation.
(II.) Sometimes the ion is soluble (as an independently variable
component) in the electrolytic fluid. Of course its condition in
the fluid when thus dissolved must be entirely different from its
condition when acting on an ion, in which case its quantity is not
independently variable, as we have already seen. Its diffusion in
the fluid in this state of solution is not necessarily connected with
any electrical current, and in other relations its properties may be
entirely changed. In any discussion of the internal properties of
the fluid (with respect to its fundamental equation, for example), it
would be necessary to treat it as a different substance. (See
page 63.) But if the process by which the charge of electricity
passes into the electrode, and the ion is dissolved in the electrolyte
is reversible, we may evidently regard the potentials for the substance
of the ion in (687) or (688) as relating to the substance thus dissolved
in the electrolyte. In case of absolute equilibrium, the density of
the substance thus dissolved would of course be uniform throughout
the fluid (since it can move independently of any electrical current),
so that by the strict application of our principle we only obtain the
somewhat barren result that if any of the ions are soluble in
the fluid without their electrical charges, the electromotive force
must vanish in any case of absolute equilibrium not dependent upon
passive resistances. Nevertheless, cases in which the ion is thus
dissolved in the electrolytic fluid only to a very small extent, and
its passage from one electrode to the other by ordinary diffusion is
extremely slow, may be regarded as approximating to the case in
which it is incapable of diffusion. In such cases, we may regard
the relations (687), (688) as approximately valid, although the
condition of equilibrium relating to the diffusion of the dissolved
ion is not satisfied. This may be the case with hydrogen and oxygen
as ions (or apparent ions) between electrodes of platinum in some
of its forms.
(III.) The ion may appear in mass at the electrode. If it be a
conductor of electricity, it may be regarded as forming an electrode,
as soon as the deposit has become thick enough to have the properties
of matter in mass. The case therefore will not be different from that
first considered. When the ion is a non-conductor, a continuous thick
deposit on the electrode would of course prevent the possibility of an
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 335
electrical current. But the case in which the ion being a non-
conductor is disengaged in masses contiguous to the electrode but
not entirely covering it, is an important one. It may be illustrated
by hydrogen appearing in bubbles at a cathode. In case of perfect
equilibrium, independent of passive resistances, the potential of the
ion in (687) or (688) may be determined in such a mass. Yet the
circumstances are quite unfavorable for the establishment of perfect
equilibrium, unless the ion is to some extent absorbed by the electrode
or electrolytic fluid, or the electrode is fluid. For if the ion must pass
immediately into the non-conducting mass, while the electricity passes
into the electrode, it is evident that the only possible terminus of an
electrolytic current is at the line where the electrode, the non-conduct-
ing mass, and the electrolytic fluid meet, so that the electrolytic
process is necessarily greatly retarded, and an approximate ceasing of
the current cannot be regarded as evidence that a state of approximate
equilibrium has been reached. But even a slight degree of solubility
of the ion in the electrolytic fluid or in the electrode may greatly
diminish the resistance to the electrolytic process, and help toward
producing that state of complete equilibrium which is supposed in the
theorem we are discussing. And the mobility of the surface of a
liquid electrode may act in the same way. When the ion is absorbed
by the electrode, or by the electrolytic fluid, the case of course comes
under the heads which we have already considered, yet the fact that
the ion is set free in mass is important, since it is in such a mass that
the determination of the value of the potential will generally be most
easily made.
(IV.) When the ion is not absorbed either by the electrode or by
the electrolytic fluid, and is not set free in mass, it may still be
deposited on the surface of the electrode. Although this can take
place only to a limited extent (without forming a body having the
properties of matter in mass), yet the electro-chemical equivalents of
all substances are so small that a very considerable flux of electricity
may take place before the deposit will have the properties of matter
in mass. Even when the ion appears in mass, or is absorbed by the
electrode or electrolytic fluid, the non-homogeneous film between the
electrolytic fluid and the electrode may contain an additional portion
of it. Whether the ion is confined to the surface of the electrode or
not, we may regard this as one of the cases in which we have to
recognize a certain superficial density of substances at surfaces of
discontinuity, the general theory of which we have already considered.
The deposit of the ion will affect the superficial tension of the
electrode if it is liquid, or the closely related quantity which we have
denoted by the same symbol a- (see pages 314-331) if the electrode is
solid. The effect can of course be best observed in the case of a liquid
336 EQUILIBEIUM OF HETEROGENEOUS SUBSTANCES.
electrode. But whether the electrodes are liquid or solid, if the
external electromotive force V— V" applied to an electrolytic com-
bination is varied, when it is too weak to produce a lasting current,
and the electrodes are thereby brought into a new state of polarization
in which they make equilibrium with the altered value of the electro-
motive force, without change in the nature of the electrodes or of the
electrolytic fluid, then by (508) or (675)
and by (687),
Hence
d( V - V") = ^dcr' - ^-,d<r". (689)
J- a •*- a
If we suppose that the state of polarization of only one of the elec-
trodes is affected (as will be the case when its surface is very small
compared with that of the other), we have
d</ = ^(F'-F"). (690)
**a
The superficial tension of one of the electrodes is then a function of
the electromotive force.
This principle has been applied by M. Lippmann to the construction
of the electrometer which bears his name.* In applying equations
(689) and (690) to dilute sulphuric acid between electrodes of
mercury, as in a Lippmann's electrometer, we may suppose that the
suffix refers to hydrogen. It will be most convenient to suppose the
dividing surface to be so placed as to make the surface-density of
mercury zero. (See page 234.) The matter which exists in excess
or deficiency at the surface may then be expressed by the surface-
densities of sulphuric acid, of water, and of hydrogen. The value
of the last may be determined from equation (690). According to
M. Lippmann's determinations, it is negative when the surface is in
its natural state (i.e., the state to which it tends when no external
electromotive force is applied), since cr' increases with V" — V. When
V" — V is equal to nine-tenths of the electromotive force of a Daniell's
cell, the electrode to which V" relates remaining in its natural state,
the tension &' of the surface of the other electrode has a maximum
value, and there is no excess or deficiency of hydrogen at that surface.
This is the condition toward which a surface tends when it is extended
while no flux of electricity takes place. The flux of electricity per
unit of new surface formed, which will maintain a surface in a
*See his memoir: "Relations entre les phenomenes electriques et capillaires,"
Annales de Chimie et de Physique, 5* se"rie, t. v, p. 494.
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 337
I"
constant condition while it is extended, is represented by in
aa
numerical value, and its direction, when Fa' is negative, is from the
mercury into the acid.
We have so far supposed, in the main, that there are no passive
resistances to change, except such as vanish with the rapidity of the
processes which they resist. The actual condition of things with
respect to passive resistances appears to be nearly as follows. There
does not appear to be any passive resistance to the electrolytic process
by which an ion is transferred from one electrode to another, except
such as vanishes with the rapidity of the process. For, in any case
of equilibrium, the smallest variation of the externally applied electro-
motive force appears to be sufficient to cause a (temporary) electrolytic
current. But the case is not the same with respect to the molecular
changes by which the ion passes into new combinations or relations,
as when it enters into the mass of the electrodes, or separates itself
in mass, or is dissolved (no longer with the properties of an ion) -in
the electrolytic fluid. In virtue of the passive resistance to these
processes, the external electromotive force may often vary within wide
limits, without creating any current by which the ion is transferred
from one of the masses considered to the other. In other words, the
value of V — V" may often differ greatly from that obtained from
(687) or (688) when we determine the values of the potentials for the
ion as in cases I, II, and III. We may, however, regard these equa-
tions as entirely valid, when the potentials for the ions are determined
at the surface of the electrodes with reference to the ion in the
condition in which it is brought there or taken away by an electrolytic
current, without any attendant irreversible processes. But in a
complete discussion of the properties of the surface of an electrode it
may be necessary to distinguish (both in respect to surface-densities
and to potentials) between the substance of the ion in this condition
and the same substance in other conditions into which it cannot pass
(directly) without irreversible processes. No such distinction, how-
ever, is necessary when the substance of the ion can pass at the
surface of the electrode by reversible processes from any one of the
conditions in which it appears to any other.
The formulae (687), (688) afford as many equations as there are ions.
These, however, amount to only one independent equation additional
to those which relate to the independently variable components of the
electrolytic fluid. This appears from the consideration that a flux of
any cation may be combined with a flux of any anion in the same
direction so as to involve no electrical current, and that this may be
regarded as the flux of an independently variable component of the
electrolytic fluid.
G.I. Y
338 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
General Properties of a Perfect Electro-chemical Apparatus.
When an electrical current passes through a galvanic or electro-
lytic cell, the state of the cell is altered. If no changes take place in
the cell except during the passage of the current, and all changes
which accompany the current can be reversed by reversing the
current, the cell may be called a perfect electro-chemical apparatus.
The electromotive force of the cell may be determined by the
equations which have just been given. But some of the general
relations to which such an apparatus is subject may be conveniently
stated in a form in which the ions are not explicitly mentioned.
In the most general case, we may regard the cell as subject to
external action of four different kinds. (1) The supply of electricity
at one electrode and the withdrawal of the same quantity at the
other. (2) The supply or withdrawal of a certain quantity of heat.
(3) The action of gravity. (4) The motion of the surfaces enclosing
the apparatus, as when its volume is increased by the liberation of
gases.
The increase of the energy in the cell is necessarily equal to that
which it receives from external sources. We may express this by the
equation
de = (V- W'yde+dQ+dWe+dWf, (691)
in which de denotes the increment of the intrinsic energy of the cell,
de the quantity of electricity which passes through it, V and V"
the electrical potentials in masses of the same kind of metal con-
nected with the anode and cathode respectively, dQ the heat received
from external bodies, dWG the work done by gravity, and dWP the
work done by the pressures which act on the external surface of the
apparatus.
The conditions under which we suppose the processes to take
place are such that the increase of the entropy of the apparatus is
equal to the entropy which it receives from external sources. The
only external source of entropy is the heat which is communicated
to the cell by the surrounding bodies. If we write drj for the
increment of entropy in the cell, and t for the temperature, we have
(692)
Eliminating dQ, we obtain
(693)
or
v,, v,_ de dr\ dWG f
v —v = — -j--\-t -j-H — j -- — -j — . (toy4)
de de de de
It is worth while to notice that if we give up the condition of the
reversibility of the processes, so that the cell is no longer supposed
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 339
to be a perfect electro-chemical apparatus, the relation (691) will
still subsist. But, if we still suppose, for simplicity, that all parts
of the cell have the same temperature, which is necessarily the case
with a perfect electro-chemical apparatus, we shall have, instead
of (692),
dn^> (695)
and instead of (693), (694)
(696)
The values of the several terms of the second member of (694)
for a given cell, will vary with the external influences to which
the cell is subjected. If the cell is enclosed (with the products of
electrolysis) in a rigid envelop, the last term will vanish. The term
relating to gravity is generally to be neglected. If no heat is
supplied or withdrawn, the term containing drj will vanish. But
in the calculation of the electromotive force, which is the most
important application of the equation, it is generally more convenient
to suppose that the temperature remains constant.
The quantities expressed by the terms containing dQ and dr\ in
(691), (693), (694), and (696) are frequently neglected in the con-
sideration of cells of which the temperature is supposed to remain
constant. In other words, it is frequently assumed that neither
heat nor cold is produced by the passage of an electrical current
through a perfect electro-chemical combination (except that heat
which may be indefinitely diminished by increasing the time in
which a given quantity of electricity passes), and that only heat
can be produced in any cell, unless it be by processes of a secondary
nature, which are not immediately or necessarily connected with
the process of electrolysis.
It does not appear that this assumption is justified by any sufficient
reason. In fact, it is easy to find a case in which the electromotive
force is determined entirely by the term t-^- in (694), all the other
terms in the second member of the equation vanishing. This is true
of a Grove's gas battery charged with hydrogen and nitrogen. In
this case, the hydrogen passes over to the nitrogen, — a process which
does not alter the energy of the cell, when maintained at a constant
temperature. The work done by external pressures is evidently
nothing, and that done by gravity is (or may be) nothing. Yet an
electrical current is produced. The work done (or which may be
done) by the current outside of the cell is the equivalent of the work
(or of a part of the work) which might be gained by allowing the
gases to mix in other ways. This is equal, as has been shown by
340 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
Lord Rayleigh,* to the work which may be gained by allowing each
gas separately to expand at constant temperature from its initial
volume to the volume occupied by the two gases together. The
same work is equal, as appears from equations (278), (279) on page
156 (see also page 159), to the increase of the entropy of the system
multiplied by the temperature.
It is possible to vary the construction of the cell in such a way
that nitrogen or other neutral gas will not be necessary. Let the
cell consist of a U-shaped tube of sufficient height, and have pure
hydrogen at each pole under very unequal pressures (as of one and two
atmospheres respectively) which are maintained constant by properly
weighted pistons, sliding in the arms of the tube. The difference of
the pressures in the gas-masses at the two electrodes must of course
be balanced by the difference in the height of the two columns of
acidulated water. It will hardly be doubted that such an apparatus
would have an electromotive force acting in the direction of a current
which would carry the hydrogen from the denser to the rarer mass.
Certainly the gas could not be carried in the opposite direction by
an external electromotive force without the expenditure of as much
(electromotive) work as is equal to the mechanical work necessary
to pump the gas from the one arm of the tube to the other. - And
if by any modification of the metallic electrodes (which remain
unchanged by the passage of electricity) we could reduce the passive
resistances to zero, so that the hydrogen could be carried reversibly
from one mass to the other without finite variation of the electro-
motive force, the only possible value of the electromotive force would
be represented by the expression t -J, as a very close approximation.
It will be observed that although gravity plays an essential part
in a cell of this kind by maintaining the difference of pressure in
the masses of hydrogen, the electromotive force cannot possibly be
ascribed to gravity, since the work done by gravity, when hydrogen
passes from the denser to the rarer mass, is negative.
Again, it is entirely improbable that the electrical currents caused
by differences in the concentration of solutions of salts (as in a cell
containing sulphate of zinc between zinc electrodes, or sulphate of
copper between copper electrodes, the solution of the salt being of
unequal strength at the two electrodes), which have recently been
investigated theoretically and experimentally by MM. Helmholtz and
Moser,t are confined to cases in which the mixture of solutions of
different degrees of concentration will produce heat. Yet in cases in
which the mixture of more and less concentrated solutions is not
* Philosophical Magazine, vol. xlix, p. 311.
t Annalen der Phyeik und Chemie, Neue Folge, Band iii, February, 1878.
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 341
attended with evolution or absorption of heat, the electromotive force
must vanish in a cell of the kind considered, if it is determined
simply by the diminution of energy in the cell. And when the
mixture produces cold, the same rule would make any electromotive
force impossible except in the direction which would tend to increase
the difference of concentration. Such conclusions would be quite
irreconcilable with the theory of the phenomena given by Professor
Helmholtz.
A more striking example of the necessity of taking account of the
variations of entropy in the cell in a priori determinations of electro-
motive force is afforded by electrodes of zinc and mercury in a
solution of sulphate of zinc. Since heat is absorbed when zinc is
dissolved in mercury,* the energy of the cell is increased by a transfer
of zinc to the mercury, when the temperature is maintained constant.
Yet in this combination, the electromotive force acts in the direction of
the current producing such a transfer.! The couple presents certain
anomalies when a considerable quantity of zinc is united with the
mercury. The electromotive force changes its direction, so that this
case is usually cited as an illustration of the principle that the electro-
motive force is in the direction of the current which diminishes the
energy of the cell, i.e., which produces or allows those changes which
are accompanied by evolution of heat when they take place directly.
But whatever may be the cause of the electromotive force which has
been observed acting in the direction from the amalgam through the
electrolyte to the zinc (a force which according to the determinations
of M. Gaugain is only one twenty-fifth part of that which acts in the
reverse direction when pure mercury takes the place of the amalgam),
these anomalies can hardly affect the general conclusions with which
alone we are here concerned. If the electrodes of a cell are pure
zinc and an amalgam containing zinc not in excess of the amount
which the mercury will dissolve at the temperature of the experiment
without losing its fluidity, and if the only change (other than thermal)
accompanying a current is a transfer of zinc from one electrode to
the other, — conditions which may not have been satisfied in all the
experiments recorded, but which it is allowable to suppose in a
theoretical discussion, and which certainly will not be regarded as
inconsistent with the fact that heat is absorbed when zinc is dissolved
in mercury, —it is impossible that the electromotive force should be
in the direction of a current transferring zinc from the amalgam to
the electrode of pure zinc. For, since the zinc eliminated from the
amalgam by the electrolytic process might be re-dissolved directly,
* J. Regnauld, Comptes Rendus, t. li, p. 778.
t Gaugain, Comptes Rendus, t. xlii, p. 430.
342 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
such a direction of the electromotive force would involve the pos-
sibility of obtaining an indefinite amount of electromotive work, and
therefore of mechanical work, without other expenditure than that of
heat at the constant temperature of the cell.
None of the cases which we have been considering involve com-
binations by definite proportions, and, except in the case of the cell
with electrodes of mercury and zinc, the electromotive forces are
quite small. It may perhaps be thought that with respect to those
cells in which combinations take place by definite proportions the
electromotive force may be calculated with substantial accuracy from
the diminution of the energy, without regarding, the variation of
entropy. But the phenomena of chemical combination do not in
general seem to indicate any possibility of obtaining from the combin-
ation of substances by any process whatever an amount of mechanical
work which is equivalent to the heat produced by the direct union of
the substances.
A kilogramme of hydrogen, for example, combining by combustion
under the pressure of the atmosphere with eight kilogrammes of
oxygen to form liquid water, yields an amount of heat which may be
represented in round numbers by 34000 calories.* We may suppose
that the gases are taken at the temperature of 0° C., and that the
water is reduced to the same temperature. But this heat cannot be
obtained at any temperature desired. A very high temperature has
the effect of preventing to a greater or less extent, the combination of
the elements. Thus, according to M. Sainte-Claire Deville,t the tem-
perature obtained by the combustion of hydrogen and oxygen cannot
much if at all exceed 2500° C., which implies that less than one-half
of the hydrogen and oxygen present combine at that temperature.
This relates to combustion under the pressure of the atmosphere.
According to the determinations of Professor BunsenJ in regard
to combustion in a confined space, only one-third of a mixture of
hydrogen and oxygen will form a chemical compound at the tem-
perature of 2850° C. and a pressure of ten atmospheres, and only a
little more than one-half when the temperature is reduced by the
addition of nitrogen to 2024° C., and the pressure to about three
atmospheres exclusive of the part due to the nitrogen.
Now 10 calories at 2500° C. are to be regarded as reversibly con-
vertible into one calorie at 4° C. together with the mechanical work
representing the energy of 9 calories. If, therefore, all the 34000
calories obtainable from the union of hydrogen and oxygen under
atmospheric pressure could be obtained at the temperature of
* See Riihlmann's Handbuch der mechanischen Warmetheorie, Bd. ii, p. 290.
tComptes Rendus, t. Ivi, p. 199; and t. Ixiv, 67.
\ Pogg. Ann., Bd. cxxxi (1867), p. 161.
EQUILIBEIUM OF HETEKOGENEOUS SUBSTANCES. 343
2500° C., and no higher, we should estimate the electromotive work
performed in a perfect electro-chemical apparatus in which these
elements are combined or separated at ordinary temperatures and
under atmospheric pressure as representing nine-tenths of the 34000
calories, and the heat evolved or absorbed in the apparatus as
representing one -tenth of the 34000 calories. * This, of course, would
give an electromotive force exactly nine-tenths as great as is obtained
on the supposition that all the 34000 calories are convertible into
electromotive or mechanical work. But, according to all indications,
the estimate 2500° C. (for the temperature at which we may regard
all the heat of combustion as obtainable) is far too high,t and
we must regard the theoretical value of the electromotive force
necessary to electrolyze water as considerably less than nine-tenths
of the value obtained on the supposition that it is necessary for
the electromotive agent to supply all the energy necessary for the
process.
The case is essentially the same with respect to the electrolysis of
hydrochloric acid, which is probably a more typical example of the
process than the electrolysis of water. The phenomenon of dissocia-
tion is equally marked, and occurs at a much lower temperature, more
than half of the gas being dissociated at 1400° C.} And the heat
which is obtained by the combination of hydrochloric acid gas with
water, especially with water which already contains a considerable
quantity of the acid, is probably only to be obtained at tempera-
tures comparatively low. This indicates that the theoretical value
of the electromotive force necessary to electrolyze this acid (i.e.,
the electromotive force which would be necessary in a reversible
electro-chemical apparatus) must be very much less than that which
could perform in electromotive work the equivalent of all the heat
evolved in the combination of hydrogen, chlorine and water to form
the liquid submitted to electrolysis. This presumption, based upon
* These numbers are not subject to correction for the pressure of the atmosphere,
since the 34000 calories relate to combustion under the same pressure.
t Unless the received ideas concerning the behavior of gases at high temperatures
are quite erroneous, it is possible to indicate the general character of a process
(involving at most only such difficulties as are neglected in theoretical discussions) by
which water may be converted into separate masses of hydrogen and oxygen without
other expenditure than that of an amount of heat equal to the difference of energy of
the matter in the two states and supplied at a temperature far below 2500° C. The
essential parts of the process would be (1) vaporizing the water and heating it to a
temperature at which a considerable part will be dissociated, (2) the partial separation
of the hydrogen and oxygen by filtration, and (3) the cooling of both gaseous masses
until the vapor they contain is condensed. A little calculation will show that in a
continuous process all the heat obtained in the operation of cooling the products of
filtration could be utilized in heating fresh water.
£ Sainte-Claire Deville, Comptes Rend.us, t. Ixiv, p. 67.
344 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
the phenomena exhibited in the direct combination of the substances,
is corroborated by the experiments of M. Favre, who has observed an
absorption of heat in the cell in which this acid was electrolyzed.*
The electromotive work expended must therefore have been less than
the increase of energy in the cell.
In both cases of composition in definite proportions which we have
considered, the compound has more entropy than its elements, and
the difference is by no means inconsiderable. This appears to be the
rule rather than the exception with respect to compounds which have
less energy than their elements. Yet it would be rash to assert that
it is an invariable rule. And when one substance is substituted for
another in a compound, we may expect great diversity in the relations
of energy and entropy.
In some cases there is a striking correspondence between the electro-
motive force of a cell and the rate of diminution of its energy per unit
of electricity transmitted, the temperature remaining constant. A
Daniell's cell is a notable example of this correspondence. It may
perhaps be regarded as a very significant case, since of all cells in
common use, it has the most constant electromotive force, and most
nearly approaches the condition of reversibility. If we apply our
previous notation (compare (691)) with the substitution of finite for
infinitesimal differences to the determinations of M. Favre, t estimating
energy in calories, we have for each equivalent (32*6 kilogrammes) of
zinc dissolved
(V- 7')Ae = 24327caL, Ae = -25394ca1-, AQ = -1067^-.
It will be observed that the electromotive work performed by the cell
is about four per cent, less than the diminution of energy in the cell4
The value of AQ, which, when negative, represents the heat evolved
in the cell when the external resistance of the circuit is very great,
was determined by direct measurement, and does not appear to have
been corrected for the resistance of the cell. This correction would
diminish the value of — AQ, and increase that of ( V" — F') Ae, which
was obtained by subtracting — AQ from — Ae.
It appears that under certain conditions neither heat nor cold
is produced in a Grove's cell. For M. Favre has found that with
different degrees of concentration of the nitric acid sometimes heat
* See M6moire8 des Savants Etrangers, se'r. 2, t. xxv, no. 1, p. 142 ; or Comptes Rendus,
t. Ixxiii, p. 973. The figures obtained by M. Favre will be given hereafter, in connec-
tion with others of the same nature.
t See M6m. Savants Etrang. , loc. cit. , p. 90 ; or Comptes Rendus, t. Ixix, p. 35, where
the numbers are slightly different.
£ A comparison of the experiments of different physicists has in some cases given a
much closer correspondence. See Wiedemann's Galvanismus, etc., 2te Auflage, Bd. ii,
§§1117, 1118.
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 345
and sometimes cold is produced.* When neither is produced, of course
the electromotive force of the cell is exactly equal to its diminution
of energy per unit of electricity transmitted. But such a coincidence
is far less significant than the fact that an absorption of heat has been
observed. With acid containing about seven equivalents of water
(HNO6+7HO) [HNO3+3JH2O], M. Favre has found
(V"- V')ke = 46781caL, Ae = -41824caL, AQ = 4957ca1;,;
and with acid containing about one equivalent of water
(HNO6+HO) [HNO3+ JH2O],
( vff - V) Ae = 49847cal- , Ae = - 52714cal , AQ = - 2867caL .
In the first example, it will be observed that the quantity of heat
absorbed in the cell is not small, and that the electromotive force is
nearly one-eighth greater than can be accounted for by the diminution
of energy in the cell.
This absorption of heat in the cell he has observed in other cases,
in which the chemical processes are much more simple.
For electrodes of cadmium and platinum in hydrochloric acid his
experiments givet
(F"_ F')Ae = 9256caL, Ae= -8258ca1-,
AFp= -290^-, AQ = 1288caL.
In this case the electromotive force is nearly one-sixth greater than
can be accounted for by the diminution of energy in the cell with the
work done against the pressure of the atmosphere.
For electrodes of zinc and platinum in the same acid one series of
experiments gives \
(V- F')Ae = 16950ca1-, Ae= -16189cal ,
AFP= -290cal, AQ = 1051cal ;
i
and a later series, §
(7"_ F')Ae = 16738caL, Ae= -17702^,
A WP = - 290cal- , AQ = - 674caL .
In the electrolysis of hydrochloric acid in a cell with a porous
partition, he has found \\
= 2113caU,
* M6m Savants Etrang., loc. cit., p. 93; or Comptes Eendus, t. Ixix, p. 37, and
t. Ixxiii, p. 893.
t Comptes Rendus, t. Ixviii, p. 1305. The total heat obtained in the whole circuit
(including the cell) when all the electromotive work is turned into heat, was ascertained
by direct experiment. This quantity, 7968 calories, is evidently represented by
( V" - V) Ae - AQ, also by - Ae + A Wf . (See (691 ). ) The value of ( V" - V) Ae is obtained
by adding A$, and that of - Ae by adding - A Wf , which is easity estimated, being
determined by the evolution of one kilogramme of hydrogen.
I Ibid.
§ M4m. Savants Etrang. , loc. cit. , p. 145.
\\Ibid., p. 142.
346 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
whence
We cannot assign a precise value to ATFP, since the quantity of
chlorine which was evolved in the form of gas is not stated. But
the value of -ATFP must lie between 290cal- and 580caL, probably
nearer to the former.
The great difference in the results of the two series of experiments
relating to electrodes of zinc and platinum in hydrochloric acid is
most naturally explained by supposing some difference in the con-
ditions of the experiment, as in the concentration of the acid, or in
the extent to which the substitution of zinc for hydrogen took place.*
That which it is important for us to observe in all these cases is that
there are conditions under which heat is absorbed in a galvanic or
electrolytic cell, so that the galvanic cell has a greater electromotive
force than can be accounted for by the diminution of its energy, and
the operation of electrolysis requires a less electromotive force than
would be calculated from the increase of energy in the cell, — especially
when the work done against the pressure of the atmosphere is taken
into account.
It should be noticed that in all these experiments the quantity
represented by AQ (which is the critical quantity with respect to
the point at issue) was determined by direct measurement of the heat
absorbed or evolved by the cell when placed alone in a calorimeter.
The resistance of the circuit was made so great by a rheostat placed
outside of the calorimeter that the resistance of the cell was regarded
as insignificant in comparison, and no correction appears to have been
made in any case for this resistance. With exception of the' error
due to this circumstance, which would in all cases diminish the heat
absorbed in the cell (or increase the heat evolved), the probable error
of AQ must be very small in comparison with that of (V'—V")Ae,
or with that of Ae, which were in general determined by the com-
parison of different calorimetrical measurements, involving very much
greater quantities of heat.
In considering the numbers which have been cited, we should
remember that when hydrogen is evolved as gas the process is in
general very far from reversible. In a perfect electrochemical
*It should perhaps be stated that in his extended memoir published in 1877 in the
At&moires dee Savants Strangers, in which he has presumably collected those results
of his experiments which he regards as most important and most accurate, M. Favre
does not mention the absorption of heat in a cell of this kind, or in the similar cell in
which cadmium takes the place of zinc. This may be taken to indicate a decided
preference for the later experiments which showed an evolution of heat. Whatever
the ground of this preference may have been, it can hardly destroy the significance
of the absorption of heat, which was a matter of direct observation in repeated experi-
ments. See Comptes Rendus, t. Ixviii, p. 1305.
EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES. 347
apparatus, the same changes in the cell would yield a much greater
amount of electromotive work, or absorb a much less amount. In
either case, the value of AQ would be much greater than in the
imperfect apparatus, the difference being measured perhaps by
thousands of calories.*
It often occurs in a galvanic or electrolytic cell that an ion which
is set free at one of the electrodes appears in part as gas, and is in
part absorbed by the electrolytic fluid, and in part absorbed by the
electrode. In such cases, a slight variation in the circumstances,
which would not sensibly affect the electromotive force, would cause
all of the ion to be disposed of in one of the three ways mentioned,
if the current were sufficiently weak. This would make a con-
siderable difference in the variation of energy in the cell, and the
electromotive force cannot certainly be calculated from the variation
of energy alone in all these cases. The correction due to the work
performed against the pressure of the atmosphere when the ion
is set free as gas will not help us in reconciling these differences.
It will appear on consideration that this correction will in general
increase the discordance in the values of the electromotive force.
Nor does it distinctly appear which of these cases is to be regarded
* Except in the case of the Grove's cell, in which the reactions are quite complicated,
the absorption of heat is most marked in the electrolysis of hydrochloric acid. The
latter case is interesting, since the experiments confirm the presumption afforded by
the behavior of the substances in other circumstances. (See page 343. ) In addition
to the circumstances mentioned above tending to diminish the observed absorption of
heat, the following, which are peculiar to this case, should be noticed.
The electrolysis was performed in a cell with a porous partition, in order to prevent
the chlorine and hydrogen dissolved in the liquid from coming in contact with each
other. It had appeared in a previous series of experiments (M4m. Savants Etrang.,
loc. cit., p. 131 ; or Comptes Rendus, t. Ixvi, p. 1231), that a very considerable amount
of heat might be produced by the chemical union of the gases in solution. In a cell
without partition, instead of an absorption, an evolution of heat took place, which
sometimes exceeded 5000 calories. If, therefore, the partition did not perfectly perform
its office, this could only cause a diminution in the value of AQ.
A large part at least of the chlorine appears to have been absorbed by the electrolytic
fluid. It is probable that a slight difference in the circumstances of the experiment —
a diminution of pressure, for example, — might have caused the greater part of the
chlorine to be evolved as gas, without essentially affecting the electromotive force.
The solution of chlorine in water presents some anomalies, and may be attended with
complex reactions, but it appears to be always attended with a very considerable
evolution of heat. (See Berthelot, Comptes Eendiis, t. Ixxvi, p. 1514.) If we regard
the evolution of the chlorine in the form of gas as the normal process, we may suppose
that the absorption of heat in the cell was greatly diminished by the retention of the
chlorine in solution.
Under certain circumstances, oxygen is evolved in the electrolysis of dilute hydro-
chloric acid. It does not appear that this took place to any considerable extent in the
experiments which we are considering. But so far as it may have occurred, we may
regard it as a case of the electrolysis of water. The significance of the fact of the
absorption of heat is not thereby affected.
348 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
as normal and which are to be rejected as involving secondary
processes.*
If in any case secondary processes are excluded, we should expect
it to be when the ion is identical in substance with the electrode upon
which it is deposited, or from which it passes into the electrolyte.
But even in this case we do not escape the difficulty of the different
forms in which the substance may appear. If the temperature of the
experiment is at the melting point of a metal which forms the ion
and the electrode, a slight variation of temperature will cause the
ion to be deposited in the solid or in the liquid state, or, if the current
is in the opposite direction, to be taken up from a solid or from a
liquid body. Since this will make a considerable difference in the
variation of energy, we obtain different values for the electromotive
force above and below the melting point of the metal, unless we
also take account of the variations of entropy. Experiment does
not indicate the existence of any such difference,! and when we take
account of variations of entropy, as in equation (694), it is apparent
Ci (• CM W
that there ought not to be any, the terms -T- and t-^- being both
affected by the same difference, viz., the heat of fusion of an electro-
chemical equivalent of the metal. In fact, if such a difference existed,
it would be easy to devise arrangements by which the heat yielded
by a metal in passing from the liquid to the solid state could be
transformed into electromotive work (and therefore into mechanical
work) without other expenditure.
The foregoing examples will be sufficient, it is believed, to show
the necessity of regarding other considerations in determining the
electromotive force of a galvanic or electrolytic cell than the variation
of its energy alone (when its temperature is supposed to remain con-
stant), or corrected only for the work which may be done by external
* It will be observed that in using the formulae (694) and (696) we do not have to
make any distinction between primary and secondary processes. The only limitation
to the generality of these formulae depends upon the reversibility of the processes,
and this limitation does not apply to (696).
t M. Raoult has experimented with a galvanic element having an electrode of bis-
muth in contact with phosphoric acid containing phosphate of bismuth in solution.
(See Comptes J&ndus, t. Ixviii, p. 643.) Since this metal absorbs in melting 12*64
calories per kilogramme or 885 calories per equivalent (70ki1-), while a Daniell's cell
yields about 24000 calories of electromotive work per equivalent of metal, the solid or
liquid state of the bismuth ought to make a difference of electromotive force repre-
sented by '037 of a Daniell's cell, if the electromotive force depended simply upon the
energy of the cell. But in M. Raoult's experiments no sudden change of electromotive
force was manifested at the moment when the bismuth changed its state of aggrega-
tion. In fact, a change of temperature in the electrode from about fifteen degrees
above to about fifteen degrees below the temperature of fusion only occasioned a
variation of electromotive force equal to '002 of a Daniell's cell.
Experiments upon lead and tin gave similar results.
EQUILIBRIUM OF HETEROGENEOUS SUBSTANjCES. 349
pressures or by gravity. But the relations expressed by (693), (694),
and (696) may be put in a briefer form.
If we set, as on page 89,
i/r = e-fy,
we have, for any constant temperature,
d\/s — de — tdri\
and for any perfect electro-chemical apparatus, the temperature of
which is maintained constant,
F'_F=_^+^o+d^p; (697)
de de de
and for any cell whatever, when the temperature is maintained uni-
form and constant,
(F'-F^^-ety + dWQ + dWP. (698)
In a cell of any ordinary dimensions, the work done by gravity, as
well as the inequalities of pressure in different parts of the cell may
be neglected. If the pressure as well as the temperature is main-
tained uniform and constant, and we set, as on page 91,
where p denotes the pressure in the cell, and v its total volume (in-
cluding the products of electrolysis), we have
dg = de — t dr\ +p dv,
and for a perfect electro-chemical apparatus,
F'-F=-^, (699)
or for any cell,
-d (700)
[SYNOPSIS.
SYNOPSIS OF SUBJECTS TREATED.
PAGE
PRELIMINARY REMARK on the rdle of energy and entropy in the theory of
thermodynamio systems, - 55
CRITERIA OF EQUILIBRIUM AND STABILITY.
Criteria enunciated, - - 56
Meaning of the term possible variations, - - 57
Passive resistances, - - 58
Validity of the criteria, - - 58
THE CONDITIONS OF EQUILIBRIUM FOR HETEROGENEOUS MASSES IN CONTACT, WHEN
UNINFLUENCED BY GRAVITY, ELECTRICITY, DISTORTION OF THE SOLID MASSES,
OR CAPILLARY TENSIONS.
Statement of the problem, - 62
Conditions relating to equilibrium between the initially existing homogeneous
parts of the system, - 62
Meaning of the term homogeneoits, - - 63
Variation of the energy of a homogeneous mass, - 63
Choice of substances to be regarded as components.— Actual and possible
components, - - 63
Deduction of the particular conditions of equilibrium when all parts of the
system have the same components, - 64
Definition of the potentials for the component substances in the various
homogeneous masses, - - 65
Case in which certain substances are only possible components in a part of
the system, - - 66
Form of the particular conditions of equilibrium when there are relations of
convertibility between the substances which are regarded as the components
of the different masses, - - 67
Conditions relating to the possible formation of masses unlike any previously
existing, - 70
Very small masses cannot be treated by the same method as those of con-
siderable size, - 75
Sense in which formula (52) may be regarded as expressing the condition
sought, - - 75
Condition (53) is always sufficient for equilibrium, but not always necessary, - 77
A mass in which this condition is not satisfied, is at least practically unstable, 79
(This condition is farther discussed under the head of Stability. See p. 100. )
Effect of solidity of any part of the system, - - 79
Effect of additional equations of condition, - - 82
Effect of a diaphragm, — equilibrium of osmotic forces, - - 83
FUNDAMENTAL EQUATIONS.
Definition and properties, - 85
Concerning the quantities ^, %> f> - - 89
Expression of the criterion of equilibrium by means of the quantity \f>, - 90
Expression of the criterion of equilibrium in certain cases by means of the
quantity f, - 91
POTENTIALS.
The value of a potential for a substance in a given mass is not dependent on the
other substances which may be chosen to represent the composition of the mass, 92
Potentials defined so as to render this property evident, - 93
SYNOPSIS OF SUBJECTS TKEATED. 351
PAOB
In the same homogeneous mass we may distinguish the potentials for an indefinite
number of substances, each of which has a perfectly determined value. Between
the potentials for different substances in the same homogeneous mass the same
equations will subsist as between the units of these substances, • - 93
The values of potentials depend upon the arbitrary constants involved in the
definition of the energy and entropy of each elementary substance, - -95
COEXISTENT PHASES.
Definition of phases — of coexistent phases, - 96
Number of the independent variations which are possible in a system of coexistent
phases, - 96
Case of 71 -f- 1 coexistent phases, - 97
Cases of a less number of coexistent phases, - 99
INTERNAL STABILITY OF HOMOGENEOUS FLUIDS AS INDICATED BY FUNDAMENTAL
EQUATIONS.
General condition of absolute stability, - - 100
Other forms of the condition, - - 104
Stability in respect to continuous changes of phase, - 105
Conditions which characterize the limits of stability in this respect, - 1 12
GEOMETRICAL ILLUSTRATIONS.
Surfaces in which the composition of the body represented is constant, - - 1 15
Surfaces and curves in which the composition of the body represented is variable
and its temperature and pressure are constant, - -118
CRITICAL PHASES.
Definition, - 129
Number of independent variations which are possible for a critical phase while
remaining such, - - 130
Analytical expression of the conditions which characterize critical phases.—
Situation of critical phases with respect to the limits of stability, - 130
Variations which are possible under different circumstances in the condition of a
mass initially in a critical phase, - - 132
ON THE VALUES OF THE POTENTIALS WHEN THE QUANTITY OF ONE OF THE
COMPONENTS IS VERY SMALL, - 135
ON CERTAIN POINTS RELATING TO THE MOLECULAR CONSTITUTION OF BODIES.
Proximate and ultimate components, - 138
Phases of dissipated energy, - - 140
Catalysis, — perfect catalytic agent, - - 141
A fundamental equation for phases of dissipated energy may be formed from the
more general form of the fundamental equation, - - 142
The phases of dissipated energy may sometimes be the only phases the existence
of which can be experimentally verified, - 142
THE CONDITIONS OF EQUILIBRIUM FOR HETEROGENEOUS MASSES UNDER THE INFLUENCE
OF GRAVITY.
The problem is treated by two different methods :
The elements of volume are regarded as variable, - 144
The elements of volume are regarded as fixed, - - 147
FUNDAMENTAL EQUATIONS OF IDEAL GASES AND GAS-MIXTURES.
Ideal gas, - - 150
Ideal gas-mixture — Dalton's Law, - 154
Inferences in regard to potentials in liquids and solids, - - 164
Considerations relating to the increase of entropy due to the mixture of gases by
diffusion, - • '. - 165
352 SYNOPSIS OF SUBJECTS TREATED.
*
PAGE
The phases of dissipated energy of an ideal gas-mixture with components which are
chemically related, - -
Gas-mixtures with convertible components,
Case of peroxide of nitrogen, - - 175
Fundamental equations for the phases of equilibrium, - - 182
SOLIDS.
The conditions of internal and external equilibrium for solids in contact with fluids
with regard to all possible states of strain, • - 184
Strains expressed by nine differential coefficients, - - 185
Variation of energy in an element of a solid, - - 186
Deduction of the conditions of equilibrium, - - 187
Discussion of the condition which relates to the dissolving of the solid, - - 193
Fundamental equations for solids, - - - 201
Concerning solids which absorb fluids, - - 215
THEORY OF CAPILLARITY.
Surfaces of discontinuity between fluid masses.
Preliminary notions. — Surfaces of discontinuity. — Dividing surface, - 219
Discussion of the problem. — The particular conditions of equilibrium for contiguous
masses relating to temperature and the potentials which have already been
obtained are not invalidated by the influence of the surface of discontinuity. —
Superficial energy and entropy. — Superficial densities of the component sub-
stances.— General expression for the variation of the superficial energy. — Con-
dition of equilibrium relating to the pressures in the contiguous masses, - - 219
Fundamental equations for surfaces of discontinuity between fluid masses, - - 229
Experimental determination of the same, - - 231
Fundamental equations for plane surfaces, - 233
Stability of surfaces of discontinuity —
(1) with respect to changes in the nature of the surface, - - 237
(2) with respect to changes in which the form of the surface is varied, - - 242
On the possibility of the formation of a fluid of different phase within any homo-
geneous fluid, - - 252
On the possible formation at the surface where two different homogeneous fluids
meet of a fluid of different phase from either, - 258
Substitution of pressures for potentials in fundamental equations for surfaces, - 264
Thermal and mechanical relations pertaining to the extension of surfaces of dis-
continuity, - - - - , - 269
Impermeable films, - - 275
The conditions of internal equilibrium for a system of heterogeneous fluid masses
without neglect of the influence of the surfaces of discontinuity or of gravity, - 276
Conditions of stability, - - 285
On the possibility of the formation of a new surface of discontinuity where several
surfaces of discontinuity meet, - - 287
The conditions of stability for fluids relating to the formation of a new phase at a
b'ne in which three surfaces of discontinuity meet, - 289
The conditions of stability for fluids relating to the formation of a new phase at a
point where the vertices of four different masses meet, - 297
Liquid films, - - 300
Definition of an element of the film, - - 300
Each element may generally be regarded as in a state of equilibrium. — Pro-
perties of an element in such a state and sufficiently thick for its interior to
have the properties of matter in mass. — Conditions under which an exten-
sion of the film will not cause an increase of tension. — When the film has
more than one component which does not belong to the contiguous masses,
extension will in general cause an- increase of tension. — Value of the elas-
ticity of the film deduced from the fundamental equations of the surfaces
and masses. — Elasticity manifest to observation, - - 300
The elasticity of a film does not vanish at the limit at which its interior ceases
to have the properties of matter in mass, but a certain kind of instability is
developed, - - ' - 305
Application of the conditions of equilibrium already deduced for a system
under the influence of gravity (pages 281, 282) to the case of a liquid film, - 305
Concerning the formation of liquid films and the processes which lead to their
destruction. — Black spots in films of soap- water, - - - 307
EQUILIBKIUM OF HETEROGENEOUS SUBSTANCES. 353
Surfaces of discontinuity between solids and fluids.
PAGE
Preliminary notions, • 314
Conditions of equilibrium for isotropic solids, • 316
Effect of gravity, - * 319
Conditions of equilibrium in the case of crystals, - - - 320
Effect of gravity, - -323
Limitations, • 323
Conditions of equilibrium for a line at which three different masses meet, one of
which is solid, - - 326
General relations, • 328
Another method and notation, - 328
ELECTROMOTIVE FORCE.
Modification of the conditions of equilibrium by electromotive force, - - 331
Equation of fluxes. — Ions. — Electro-chemical equivalents, 331
Conditions of equilibrium, - - 332
Four cases, - 333
Lippmann's electrometer, - - 336
Limitations due to passive resistances, - 337
General properties of a perfect electro-chemical apparatus, - - 338
Reversibility the test of perfection, • . - 338
Determination of the electromotive force from the changes which take place
in the cell. — Modification of the formula for the case of an imperfect
apparatus, - - 338
When the temperature of the cell is regarded as constant, it is not allowable "
to neglect the variation of entropy due to heat absorbed or evolved. — This
is shown by a Grove's gas battery charged with hydrogen and nitrogen, 339
by the currents caused by differences in the concentration of the electrolyte, 340
and by electrodes of zinc and mercury in a solution of sulphate of zinc, 341
That the same is true when the chemical processes take place by definite
proportions is shown by a priori considerations based on the phenomena
exhibited in the direct combination of the elements of water or of hydro-
chloric acid, - 342
and by the absorption of heat which M. Favre has in many cases observed
in a galvanic or electrolytic cell, - - 345
The different physical states in which the ion is deposited do not affect the
value of the electromotive force, if the phases are coexistent. — Experiments
of M. Raoult, - . - 347
Other formulae for the electromotive force, - 349
G.I.
IV.
ON THE EQUILIBRIUM OF HETEROGENEOUS
SUBSTANCES.
ABSTRACT OF THE PRECEDING PAPER BY THE AUTHOR.
[American Journal of Science, 3 ser., vol. xvi., pp. 441-458, Dec., 1878.]
IT is an inference naturally suggested by the general increase of
entropy which accompanies the changes occurring in any isolated
material system that when the entropy of the system has reached a
maximum, the system will be in a state of equilibrium. Although
this principle has by no means escaped the attention of physicists,
its importance does not appear to have been duly appreciated. Little
has been done to develop the principle as a foundation for the general
theory of thermodynamic equilibrium.
The principle may be formulated as follows, constituting a criterion
of equilibrium : —
I. Far the equilibrium of any isolated system it is necessary and
sufficient that in all possible variations of the state of the system
which do not alter its energy, the variation of its entropy shall
either vanish or be negative. «-
The following form, which is easily shown to be equivalent to the
preceding, is often more convenient in application : —
II. For the equilibrium of any isolated system it is necessary and
sufficient that in all possible variations of the state of the system
which do not alter its entropy, the variation of its energy shall
either vanish or be positive.
If we denote the energy and entropy of the system by e and r\
respectively, the criterion of equilibrium may be expressed by either
of the formulae
W.^o, (i)
(*e),£0. (2)
Again, if we assume that the temperature of the system is uniform,
and denote its absolute temperature by t, and set
^ = €-fy, (3)
the remaining conditions of equilibrium may be expressed by the
formula
O, (4)
ABSTRACT BY THE AUTHOR. 355
the suffixed letter, as in the preceding cases, indicating that the
quantity which it represents is constant. This condition, in connection
with that of uniform temperature, may be shown to be equivalent
to (1) or (2). The difference of the values of \^ for two different
states of the system which have the same temperature represents the
work which would be expended in bringing the system from one
state to the other by a reversible process and without change of
temperature.
If the system is incapable of thermal changes, like the systems
considered in theoretical mechanics, we may regard the entropy as
having the constant value zero. Conditions (2) and (4) may then
be written
and are obviously identical in signification, since in this case \fs = e.
Conditions (2) and (4), as criteria of equilibrium, may therefore
both be regarded as extensions of the criterion employed in ordinary
statics to the more general case of a thermodynamic system. In fact,
each of the quantities — e and — \{s (relating to a system without
sensible motion) may be regarded as a kind of force-function for
the system, — the former as the force-function for constant entropy
(i.e., when only such states of the system are considered as have
the same entropy), and the latter as the force-function for constant
temperature (i.e., when only such states of the system are considered
as have the same uniform temperature).
In the deduction of the particular conditions of equilibrium for
any system, the general formula (4) has an evident advantage over
(1) or (2) with respect to the brevity of the processes of reduction,
since the limitation of constant temperature applies to every part
of the system taken separately, and diminishes by one the number
of independent variations in the state of these parts which we have
to consider. Moreover, the transition from the systems considered
in ordinary mechanics to thermodynamic systems is most naturally
made by this formula, since it has always been customary to apply
the principles of theoretical mechanics to real systems on the sup-
position (more or less distinctly conceived and expressed) that the
temperature of the system remains constant, the mechanical properties
of a thermodynamic system maintained at a constant temperature
being such as might be imagined to belong to a purely mechanical
system, and admitting of representation by a force-function, as follows
directly from the fundamental laws of thermodynamics.
Notwithstanding these considerations, the author has preferred in
general to use condition (2) as the criterion of equilibrium, believing
that it would be useful to exhibit the conditions of equilibrium of
thermodynamic systems in connection with those quantities which
356 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
are most simple and most general in their definitions, and which
appear most important in the general theory of such systems. The
slightly different form in which the subject would develop itself,
if condition (4) had been chosen as a point of departure instead of (2),
is occasionally indicated.
Equilibrium of masses in contact. — The first problem to which
the criterion is applied is the determination of the conditions of
equilibrium for different masses in contact, when uninfluenced by
gravity, electricity, distortion of the solid masses, or capillary tensions.
The statement of the result is facilitated by the following definition.
If to any homogeneous mass in a state of hydrostatic stress we
suppose an infinitesimal quantity of any substance to be added, the
mass remaining homogeneous and its entropy and volume remaining
unchanged, the increase of the energy of the mass divided by the
quantity of the substance added is the potential for that substance in
the mass considered.
In addition to equality of temperature and pressure in the masses
in contact, it is necessary for equilibrium that the potential for every
substance which is an independently variable component of any of
the different masses shall have the same value in all of which it is
such a component, so far as they are in contact with one another.
But if a substance, without being an actual component of a certain
mass in the given state of the system, is capable of being absorbed
by it, it is sufficient if the value of the potential for that substance
in that mass is not less than in any contiguous mass of which the
substance is an actual component. We may regard these conditions
as sufficient for equilibrium with respect to infinitesimal variations
in the composition and thermodynamic state of the different masses
in contact. There are certain other conditions which relate to the
possible formation of masses entirely different in composition or state
from any initially existing. These conditions are best regarded as
determining the stability of the system, and will be mentioned under
that head.
Anything which restricts the free movement of the component
substances, or of the masses as such, may diminish the number of
conditions which are necessary for equilibrium.
Equilibrium of osmotic forces. — If we suppose two fluid masses
to be separated by a diaphragm which is permeable to some of the
component substances and not to others, of the conditions of equi-
librium which have just been mentioned, those will still subsist which
relate to temperature and the potentials for the substances to which
the diaphragm is permeable, but those relating to the potentials for
the substances to which the diaphragm is impermeable will no longer
be necessary. Whether the pressure must be the same in the two
ABSTRACT BY THE AUTHOR. 357
fluids will depend upon the rigidity of the diaphragm. Even when
the diaphragm is permeable to all the components without restriction,
equality of pressure in the two fluids is not always necessary for
equilibrium.
Effect of gravity. — In a system subject to the action of gravity,
the potential for each substance, instead of having a uniform value
throughout the system, so far as the substance actually occurs as an
independently variable component, will decrease uniformly with
increasing height, the difference of its values at different levels being
equal to the difference of level multiplied by the force of gravity.
Fundamental equations. — Let e, jy, v, t and p denote respectively
the energy, entropy, volume, (absolute) temperature, and pressure of
a homogeneous mass, which may be either fluid or solid, provided
that it is subject only to hydrostatic pressures, and let m1} ra2, ... ran
denote the quantities of its independently variable components, and
fjilt //2, ... fJLn the potentials for these components. It is easily shown
that e is a function of ij, v, m1, ra2, ... ran, and that the complete .value
of de is given by the equation
de = tdq —p dv + fildm1 + /z2dm2 . . . -f nnd/mn. (5)
Now if € is known in terms of ;;, v, m1} ... mn, we can obtain by
differentiation t, p, /zx, ... fj.n in terms of the same variables. This
will make n + 3 independent known relations between the 2n + 5
variables, e, r\, v, ra^ m2, ... mn, t, p, JULV /*2, ... /xn. These are all that
exist, for of these variables, 7i+2 are evidently independent. Now
upon these relations depend a very large class of the properties of
the compound considered, — we may say in general, all its thermal,
mechanical, and chemical properties, so far as active tendencies are
concerned, in cases in which the form of the mass does not require
consideration. A single equation from which all these relations may
be deduced may be called a fundamental equation. An equation
between e, 77, v, ml, m2, ... mn is a fundamental equation. But there
are other equations which possess the same property.
If we suppose the quantity \fs to be determined for such a mass
as we are considering by equation (3), we may obtain by differentiation
and comparison with (5)
d\fs = —rjdt —p dv + fjL1dml + fJLzdm2 . . . + fjLndmn. (6)
If, then, \fs is known as a function of t, v, mx, ra2, ... mn, we can find
n> P> Pi* At2>-"/un in terms of the same variables. If we then
substitute for \[s in our original equation its value taken from
equation (3) we shall have again n+3 independent relations between
the same 2n+5 variables as before.
Let
(7)
358 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
then, by (5),
-f //2dm2 . . . -f fjLndmn. (8)
If, then, f is known as a function of t,p, mx, m2, ... mn, we can find
q, vy /Zj, /*8, .../£n in terms of the same variables. By eliminating £
we may obtain again 7i+3 independent relations between the same
271+5 variables as at first.*
If we integrate (5), (6) and (8), supposing the quantity of the
compound substance considered to vary from zero to any finite value,
its nature and state remaining unchanged, we obtain
n, (9)
, (10)
(11)
If we differentiate (9) in the most general manner, and compare the
result with (5), we obtain
— vdp + ridt+m1djUil+m2d[ji2...+mndiuin = Q, (12)
or
n Jj. , mi 7 , m2 J , m« 7 A /10\
= -dt-\ — 1 du, + — ^ du.* . . . H — ^dun = 0. (13)
1 n
V V V V
Hence, there is a relation between the 7i + 2 quantities t, p, fjL1}
/j.2, ... fjin, which, if known, will enable us to find in terms of these
quantities all the ratios of the T&+2 quantities TJ, v, m1? m2, ...mn.
With (9), this will make 7i+3 independent relations between the same
2n -f 5 variables as at first.
Any equation, therefore, between the quantities
e, q, v, m1? m2, ...mn,
or i/r, ^, v, m15 m2, ...mn,
or ^, ^, p} mj, m2,...mn,
or , p, JULI} //2, ...
is a fundamental equation, and any such is entirely equivalent to
any other.
Coexistent phases. — In considering the different homogeneous bodies
which can be formed out of any set of component substances, it is
convenient to have a term which shall refer solely to the composition
* The properties of the quantities - \f/ and - f regarded as functions of the tempera-
ture and volume, and temperature and pressure, respectively, the composition of the
body being regarded as invariable, have been discussed by M. Massieu in a memoir
entitled "Sur les fonctions caract&istiques des divers fluides et sur la th^orie des
vapours" (M6m. Savants Etrang., t. xxii). A brief sketch of his method in a form
slightly different from that ultimately adopted is given in Comptes Eendus, t. Ixix (1869),
pp. 868 and 1057, and a report on his memoir by M. Bertrand in Comptes Rendm, t. Ixxi,
p. 257. M. Massieu appears to have been the first to solve the problem of representing
all the properties of a body of invariable composition which are concerned in reversible
processes by means of a single function.
ABSTRACT BY THE AUTHOR 359
and thermodynamic state of any such body without regard to its size
or form. The word phase has been chosen for this purpose. Such
bodies as differ in composition or state are called different phases of
the matter considered, all bodies which differ only in size and form
being regarded as different examples of the same phase. Phases
which can exist together, the dividing surfaces being plane, in an
equilibrium which does not depend upon passive resistances to change,
are called coexistent.
The number of independent variations of which a system of co-
existent phases is capable is 71+2— r, where r denotes the number of
phases, and n the number of independently variable components in
the whole system. For the system of phases is completely specified
by the temperature, the pressure, and the n potentials, and between
these n+2 quantities there are r independent relations (one for each
phase), which characterize the system of phases.
When the number of phases exceeds the number of components by
unity, the system is capable of a single variation of phase. The
pressure and all the potentials may be regarded as functions of the
temperature. The determination of these functions depends upon the
elimination of the proper quantities from the fundamental equations
in p, t, /z-p yu2, etc. for the several members of the system. But
without a knowledge of these fundamental equations, the values of
the differential coefficients such as -£ may be expressed in terms of
the entropies and volumes of the different bodies and the quantities
of their several components. For this end we have only to eliminate
the differentials of the potentials from the different equations of the
form (12) relating to the different bodies. In the simplest case, when
there is but one component, we obtain the well-known formula
dp_n'-r[' Q
dt~vf-vn~~t(v"-vy
in which v', v", rf, if' denote the volumes and entropies of a given
quantity of the substance in the two phases, and Q the heat which it
absorbs in passing from one phase to the other.
It is easily shown that if the temperature of two coexistent phases
of two components is maintained constant, the pressure is in general
a maximum or minimum when the composition of the phases is
identical. In like manner, if the pressure of the phases is maintained
constant, the temperature is in general a maximum or minimum when
the composition of the phases is identical. The series of simultaneous
values of t and p for which the composition of two coexistent phases
is identical separates those simultaneous values of t and p for which
no coexistent phases are possible from those for which there are two
pairs of coexistent phases.
360 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
If the temperature of three coexistent phases of three components
is maintained constant, the pressure is in general a maximum or
minimum when the composition of one of the phases is such as can be
produced by combining the other two. If the pressure is maintained
constant, the temperature is in general a maximum or minimum when
the same condition in regard to the composition of the phases is
fulfilled.
Stability of fluids. — A criterion of the stability of a homogeneous
fluid, or of a system of coexistent fluid phases, is afforded by the
expression
€-t'q+p'v-[j.l'm1-fjL2'm2...-iuLn'mn, (14)
in which the values of the accented letters are to be determined by
the phase or system of phases of which the stability is in question,
and the values of the unaccented letters by any other phase of the
same components, the possible formation of which is in question. We
may call the former constants, and the latter variables. Now if the
value of the expression, thus determined, is always positive for any
possible values of the variables, the phase or system of phases will
be stable with respect to the formation of any new phases of its
components. But if the expression is capable of a negative value,
the phase or system is at least practically unstable. By this is meant
that, although, strictly speaking, an infinitely small disturbance or
change may not be sufficient to destroy the equilibrium, yet a very
small change in the initial state will be sufficient to do so. The
presence of a small portion of matter in a phase for which the above
expression has a negative value will in general be sufficient to produce
this result. In the case of a system of phases, it is of course supposed
that their contiguity is such that the formation of the new phase does
not involve any transportation of matter through finite distances.
The preceding criterion affords a convenient point of departure in
the discussion of the stability of homogeneous fluids. Of the other
forms in which the criterion may be expressed, the following is
perhaps the most useful : —
// the pressure of a fluid is greater than that of any other phase
of its independent variable components which has the same temper-
ature and potentials, the fluid is stable with respect to the formation
of any other phase of these components ; but if its pressure is not
as great as that of some such phase, it will be practically unstable.
Stability of fluids with respect to continuous changes of phase. —
In considering the changes which may take place in any mass,
we have often to distinguish between infinitesimal changes in existing
phases, and the formation of entirely new phases. A phase of a fluid
may be stable with respect to the former kind of change, and unstable
with respect to the latter. In this case, it may be capable of continued
ABSTKACT BY THE AUTHOR. 361
existence in virtue of properties which prevent the commencement of
discontinuous changes. But a phase which is unstable with respect to
continuous changes is evidently incapable of permanent existence on a
large scale except in consequence of passive resistances to change.
To obtain the conditions of stability with respect to continuous
changes, we have only to limit the application of the variables in (14)
to phases adjacent to the given phase. We obtain results of the
following nature.
The stability of any phase with respect to continuous changes
depends upon the same conditions with respect to the second and
higher differential coefficients of the density of energy regarded as
a function of the density of entropy and the densities of the several
components, which would make the density of energy a minimum,
if the necessary conditions with respect to the first differential
coefficients were fulfilled.
Again, it is necessary and sufficient for the stability with respect
to continuous changes of all the phases within any given limits,~that
within those limits the same conditions should be fulfilled with
respect to the second and higher differential coefficients of the
pressure regarded as a function of the temperature and the several
potentials, which would make the pressure a minimum, if the
necessary conditions with respect to the first differential coefficients
were fulfilled.
The equation of the limits of stability with respect to continuous
changes may be written
=0, or =00, (15)
where yn denotes the density of the component specified or mn-r-v.
It is in general immaterial to what component the suffix n is regarded
as relating.
Critical phases. — The variations of two coexistent phases are
sometimes limited by the vanishing of the difference between them.
Phases at which this occurs are called critical phases. A critical
phase, like any other, is capable of Ti-fl independent variations,
n denoting the number of independently variable components. But
when subject to the condition of remaining a critical phase, it is
capable of only n — 1 independent variations. There are therefore
two independent equations which characterize critical phases. These
may be written
=Q
It will be observed that the first of these equations is identical with
the equation of the limit of stability with respect to continuous
362 EQUILIBKIUM OF HETEROGENEOUS SUBSTANCES.
changes. In fact, stable critical phases are situated at that limit.
They are also situated at the limit of stability with respect to dis-
continuous changes. These limits are in general distinct, but touch
each other at critical phases.
Geometrical illustrations. — In an earlier paper,* the author has
described a method of representing the thermodynamic properties
of substances of invariable composition by means of surfaces. The
volume, entropy, and energy of a constant quantity of the substance
are represented by rectangular coordinates. This method corresponds
to the first kind of fundamental equation described above. Any
other kind of fundamental equation for a substance of invariable
composition will suggest an analogous geometrical method. In the
present paper, the method in which the coordinates represent tem-
perature, pressure, and the potential, is briefly considered. But
when the composition of the body is variable, the fundamental
equation cannot be completely represented by any surface or finite
number of surfaces. In the case of three components, if we regard
the temperature and pressure as constant, as well as the total quantity
of matter, the relations between f, m1} m2, m3 may be represented
by a surface in which the distances of a point from the three sides
of a triangular prism represent the quantities mx, m2, m3, and the
distance of the point from the base of the prism represents the
quantity £ In the case of two components, analogous relations may
be represented by a plane curve. Such methods are especially useful
for illustrating the combinations and separations of the components,
and the changes in states of aggregation, which take place when the
substances are exposed in varying proportions to the temperature
and pressure considered.
Fundamental equations of ideal gases and gas-mixtures. — From
the physical properties which we attribute to ideal gases, it is easy
to deduce their fundamental equations. The fundamental equation
in e, 77, v, and m for an ideal gas is
n e — Em r\ „ , m /1f_x
clog = — — H+aW — ; (17)
cm m ' v
that in i/r, t, v, and m is
^ = Em+m*(c-H-clog£+alog-); (18)
that in p, t, and JUL is
H-c-a c+a /u.-E
p = ae a t~^e~°rt (19)
where e denotes the base of the Naperian system of logarithms. As
for the other constants, c denotes the specific heat of the gas at
* [Page 33 of this volume.]
ABSTRACT BY THE AUTHOR 363
constant volume, a denotes the constant value of pv+mt, E and H
depend upon the zeros of energy and entropy. The two last equations
may be abbreviated by the use of different constants. The properties
of fundamental equations mentioned above may easily be verified
in each case by differentiation.
The law of Dalton respecting a mixture of different gases affords
a point of departure for the discussion of such mixtures and the
establishment of their fundamental equations. It is found convenient
to give the law the following form : —
The pressure in a mixture of different gases is equal to the sum of
the pressures of the different gases as existing each by itself at tJie
same temperature and with the same value of its potential.
A mixture of ideal gases which satisfies this law is called an
ideal gas-mixture. Its fundamental equation in p, t, filt fJL2, etc. is
evidently of the form
(20)
where 2^ denotes summation with respect to the different components
of the mixture. From this may be deduced other fundamental
equations for ideal gas-mixtures. That in \/r, t, v, m^ m2, etc. is
(21)
Phases of dissipated energy of ideal gas-mixtures. — When the
proximate components of a gas-mixture are so related that some of
them can be formed out of others, although not necessarily in the
gas-mixture itself at the temperatures considered, there are certain
phases of the gas-mixture which deserve especial attention. These
are the phases of dissipated energy, i.e., those phases in which the
energy of the mass has the least value consistent with its entropy
and volume. An atmosphere of such a phase could not furnish a
source of mechanical power to any machine or chemical engine
working within it, as other phases of the same matter might do.
Nor can such phases be affected by any catalytic agent. A perfect
catalytic agent would reduce any other phase of the gas-mixture
to a phase of dissipated energy. The condition which will make the
energy a minimum is that the potentials for the proximate com-
ponents shall satisfy an equation similar to that which expresses the
relation between the units of weight of these components. For
example, if the components were hydrogen, oxygen and water, since
one gram of hydrogen with eight grams of oxygen are chemically
equivalent to nine grams of water, the potentials for these substances
in a phase of dissipated energy must satisfy the relation
364 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
Gas-mixtures with convertible components. — The theory of the
phases of dissipated energy of an ideal gas-mixture derives an especial
interest from its possible application to the case of those gas-mixtures
in which the chemical composition and resolution of the components
can take place in the gas-mixture itself, and actually does take place,
so that the quantities of the proximate components are entirely deter-
mined by the quantities of a smaller number of ultimate components,
with the temperature and pressure. These may be called gas-mixtures
with convertible components. If the general laws of ideal gas-
mixtures apply in any such case, it may easily be shown that the
phases of dissipated energy are the only phases which can exist.
We can form a fundamental equation which shall relate solely to
these phases. For this end, we first form the equation in p, t, JJLV
fj.2, etc. for the gas-mixture, regarding its proximate components as
not convertible. This equation will contain a potential for every
proximate component of the gas-mixture. We then eliminate one (or
more) of these potentials by means of the relations which exist between
them in virtue of the convertibility of the components to which they
relate, leaving the potentials which relate to those substances which
naturally express the ultimate composition of the gas-mixture.
The validity of the results thus obtained depends upon the applica-
bility of the laws of ideal gas-mixtures to cases in which chemical
action takes place. Some of these laws are generally regarded as
capable of such application, others are not so regarded. But it may
be shown that in the very important case in which the components of
a gas are convertible at certain temperatures, and not at others, the
theory proposed may be established without other assumptions than
such as are generally admitted.
It is, however, only by experiments upon gas-mixtures with con-
vertible components, that the validity of any theory concerning them
can be satisfactorily established.
The vapor of the peroxide of nitrogen appears to be a mixture of
two different vapors, of one of which the molecular formula is double
that of the other. If we suppose that the vapor conforms to the laws
of an ideal gas-mixture in a state of dissipated energy, we may obtain
an equation between the temperature, pressure, and density of the
vapor, which exhibits a somewhat striking agreement with the results
of experiment.
Equilibrium of stressed solids. — The second part of the paper*
commences with a discussion of the conditions of internal and external
equilibrium for solids in contact with fluids with regard to all possible
states of strain of the solids. These conditions are deduced by
* [See footnote, p. 184.]
ABSTRACT BY THE AUTHOR 365
analytical processes from the general condition of equilibrium (2). The
condition of equilibrium which relates to the dissolving of the solid
at a surface where it meets a fluid may be expressed by the equation
ft-i=*±£?, (22)
where e, rj, v, and mx denote respectively the energy, entropy, volume,
and mass of the solid, if it is homogeneous in nature and state of
strain, — otherwise, of any small portion which may be treated as thus
homogeneous, — fa the potential in the fluid for the substance of which
the solid consists, p the pressure in the fluid and therefore one of the
principal pressures in the solid, and t the temperature. It will be
observed that when the pressure in the solid is isotropic, the second
member of this equation will represent the potential in the solid for
the substance of which it consists {see (9)}, and the condition reduces
to the equality of the potential in the two masses, just as if it were a
case of two fluids. But if the stresses in the solid are not isotropic,
the value of the second member of the equation is not entirely deter-
mined by the nature and state of the solid, but has in general three
different values (for the same solid at the same temperature, and in
the same state of strain) corresponding to the three principal pressures
in the solid. If a solid in the form of a right parallelepiped is subject
to different pressures on its three pairs of opposite sides by fluids in
which it is soluble, it is in general necessary for equilibrium that the
composition of the fluids shall be different.
The fundamental equations which have been described above are
limited, in their application to solids, to the case in which the stresses
in the solid are isotropic. An example of a more general form of
fundamental equation for a solid, is afforded by an equation between
the energy and entropy of a given quantity of the solid, and the
quantities which express its state of strain, or by an equation between
i/r {see (3)} as determined for a given quantity of the solid, the tem-
perature, and the quantities which express the state of strain.
Capillarity. — The solution of the problems which precede may be
regarded as a first approximation, in which the peculiar state of
thermodynamic equilibrium about the surfaces of discontinuity is
neglected. To take account of the condition of things at these
surfaces, the following method is used. Let us suppose that two
homogeneous fluid masses are separated by a surface of discontinuity,
i.e., by a very thin non-homogeneous film. Now we may imagine a
state of things in which each of the homogeneous masses extends
without variation of the densities of its several components, or of the
densities of energy and entropy, quite up to a geometrical surface (to
be called the dividing surface) at which the masses meet. We may
suppose this surface to be sensibly coincident with the physical surface
366 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
of discontinuity. Now if we compare the actual state of things with
the supposed state, there will be in the former in the vicinity of the
surface a certain (positive or negative) excess of energy, of entropy,
and of each of the component substances. These quantities are
denoted by e8, if, m?, mf, etc., and are treated as belonging to the
surface. The s is used simply as a distinguishing mark, and must not
be taken for an algebraic exponent.
It is shown that the conditions of equilibrium already obtained
relating to the temperature and the potentials of the homogeneous
masses, are not affected by the surfaces of discontinuity, and that the
complete value of Sea is given by the equation
Ses = t STJS + cr Ss + yu^m? + /*2<$mf + etc., (23)
in which s denotes the area of the surface considered, t the tempera-
ture, filt /x2, etc., the potentials for the various components in the
adjacent masses. It may be, however, that some of the components
are found only at the surface of discontinuity, in which case the letter
IUL with the suffix relating to such a substance denotes, as the equation
shows, the rate of increase of energy at the surface per unit of the
substance added, when the entropy, the area of the surface, and the
quantities of the other components are unchanged. The quantity &
we may regard as defined by the equation itself, or by the following,
which is obtained by integration : —
e8 — tqs + o-s + //! m? + //2mf + etc. (24)
There are terms relating to variations of the curvatures of the
surface which might be added, but it is shown that we can give the
dividing surface such a position as to make these terms vanish, and it
is found convenient to regard its position as thus determined. It is
always sensibly coincident with the physical surface of discontinuity.
(Yet in treating of plane surfaces, this supposition in regard to the
position of the dividing surface is unnecessary, and it is sometimes
convenient to suppose that its position is determined by other con-
siderations.)
With the aid of (23), the remaining condition of equilibrium for
contiguous homogeneous masses is found, viz.,
<r(Cl+c2) -p'-p', (25)
where p', p" denote the pressures in the two masses, and clf c2 the
principal curvatures of the surface. Since this equation has the same
form as if a tension equal to a- resided at the surface, the quantity or
is called (as is usual) the superficial tension, and the dividing surface
in the particular position above mentioned is called the surface of
tension.
By differentiation of (24) and comparison with (23), we obtain
— etc., (26)
ABSTRACT BY THE AUTHOR 367
8 8 S
where ija, Tlt F2, etc. are written for — , — , — , etc., and denote the
888
superficial densities of entropy and of the various substances. We
may regard a- as a function of t, filt fjL2, etc., from which if known
jyg, I\, F2, etc. may be determined in terms of the same variables.
An equation between a; t, fJ.lt fa, etc. may therefore be called & funda-
mental equation for the surface of discontinuity. The same may be
said of an equation between e8, q8, s, m8, raf., etc.
It is necessary for the stability of a surface of discontinuity that
its tension shall be as small as that of any other surface which can
exist between the same homogeneous masses with the same tempera-
ture and potentials. Besides this condition, which relates to the nature
of the surface of discontinuity, there are other conditions of stability,
which relate to the possible motion of such surfaces. One of these is
that the tension shall be positive. The others are of a less simple
nature, depending upon the extent and form of the surface of dis-
continuity, and in general upon the whole system of which it is a
part. The most simple case of a system with a surface of discon-
tinuity is that of two coexistent phases separated by a spherical
surface, the outer mass being of indefinite extent. When the interior
mass and the surface of discontinuity are formed entirely of sub-
stances which are components of the surrounding mass, the equilibrium
is always unstable; in other cases, the equilibrium may be stable.
Thus, the equilibrium of a drop of water in an atmosphere of vapor
is unstable, but may be made stable by the addition of a little salt.
The analytical conditions which determine the stability or instability
of the system are easily found, when the temperature and potentials
of the system are regarded as known, as well as the fundamental
equations for the interior mass and the surface of discontinuity.
The study of surfaces of discontinuity throws considerable light
upon the subject of the stability of such phases of fluids as have a
less pressure than other phases of the same components with the same
temperature and potentials. Let the pressure of the phase of which
the stability is in question be denoted by p', and that of the other
phase of the same temperature and potentials by p". A spherical
mass of the second phase and of a radius determined by the equation
2<r = Q9"-/)r, (27)
would be in equilibrium with a surrounding mass of the first phase.
This equilibrium, as we have just seen, is unstable, when the surround-
ing mass is indefinitely extended. A spherical mass a little larger
would tend to increase indefinitely. The work required to form such
a spherical mass, by a reversible process, in the interior of an infinite
mass of the other phase, is given by the equation
W = <rs-(p"-p')v". (28)
368 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
The term a-s represents the work spent in forming the surface, and
the term (p"—p')v" the work gained in forming the interior mass.
The second of these quantities is always equal to two-thirds of the
first. The value of W is therefore positive, and the phase is in
strictness stable, the quantity W affording a kind of measure of its
stability. We may easily express the value of W in a form which
does not involve any geometrical magnitudes, viz.,
™
>
where p", p' and cr may be regarded as functions of the temperature
and potentials. It will be seen that the stability, thus measured,
is infinite for an infinitesimal difference of pressures, but decreases
very rapidly as the difference of pressures increases. These con-
clusions are all, however, practically limited to the case in which
the value of r, as determined by equation (27), is of sensible
magnitude.
With respect to the somewhat similar problem of the stability
of the surface of contact of two phases with respect to the formation
of a new phase, the following results are obtained. Let the phases
(supposed to have the same temperature and potentials) be denoted
by A, B, and C ; their pressures by pA, pE and pc ; and the tensions
of the three possible surfaces by o-ABJ O"BC> OAC- If PC is IGSS than
there will be no tendency toward the formation of the new phase
at the surface between A and B. If the temperature or potentials
are now varied until pc is equal to the above expression, there are
two cases to be distinguished. The tension 0-AB will be either equal
to O-AC + <TBC or less- (A greater value could only relate to an unstable
and therefore unusual surface.) If (rAB = crAc+o-Bc> a farther variation
of the temperature or potentials, making pc greater than the above
expression, would cause the phase C to be formed at the surface
between A and B. But if OTAB < O"AC + O"BC> the surface between A and
B would remain stable, but with rapidly diminishing stability, after
pc has passed the limit mentioned.
The conditions of stability for a line where several surfaces of
discontinuity meet, with respect to the possible formation of a new
surface, are capable of a very simple expression. If the surfaces A-B,
B-C, C-D, D-A, separating the masses A, B, C, D, meet along a line,
it is necessary for equilibrium that their tensions and directions at
any point of the line should be such that a quadrilateral a, /3, y, S
may be formed with sides representing in direction and length the
normals and tensions of the successive surfaces. For the stability
ABSTRACT BY THE AUTHOR. 369
of the system with reference to the possible formation of surfaces
between A and C, or between B and D, it is farther necessary that
the tensions <rAc and O-BD should be greater than the diagonals ay and
/3S respectively. The conditions of stability are entirely analogous
in the case of a greater number of surfaces. For the conditions of
stability relating to the formation of a new phase at a line in which
three surfaces of discontinuity meet, or at a point where four different
phases meet, the reader is referred to the original paper.
Liquid films. — When a fluid exists in the form of a very thin
film between other fluids, the great inequality of its extension in
different directions will give rise to certain peculiar properties, even
when its thickness is sufficient for its interior to have the properties
of matter in mass. The most important case is where the film is
liquid and the contiguous fluids are gaseous. If we imagine the film
to be divided into elements of the same order of magnitude as its
thickness, each element extending through the film from side to side,
it is evident that far less time will in general be required for the
attainment of approximate equilibrium between the different parts
of any such element and the contiguous gases than for the attainment
of equilibrium between all the different elements of the film.
There will accordingly be a time, commencing shortly after the
formation of the film, in which its separate elements may be regarded
as satisfying the conditions of internal equilibrium, and of equilibrium
with the contiguous gases, while they may not satisfy all the con-
ditions of equilibrium with each other. It is when the changes due
to this want of complete equilibrium take place so slowly that the
film appears to be at rest, except so far as it accommodates itself to
any change in the external conditions to which it is subjected, that
the characteristic properties of the film are most striking and most
sharply defined. It is from this point of view that these bodies are
discussed. They are regarded as satisfying a certain well-defined
class of conditions of equilibrium, but as not satisfying at all certain
other conditions which would be necessary for complete equilibrium,
in consequence of which they are subject to gradual changes, which
ultimately determine their rupture.
The elasticity of a film (i.e., the increase of its tension when ex-
tended) is easily accounted for. It follows from the general relations
given above that when a film has more than one component, those
components which diminish the tension will be found in greater pro-
portion on the surfaces. When the film is extended, there will not be
enough of these substances to keep up the same volume- and surface-
densities as before, and the deficiency will cause a certain increase of
tension. It does not follow that a thinner film has always a greater
tension than a thicker formed of the same liquid. When the phases
G. I. 2A
370 EQUILIBRIUM OF HETEROGENEOUS SUBSTANCES.
within the films as well as without are the same, and the surfaces of
the films are also the same, there will be no difference of tension.
Nor will the tension of the same film be altered, if a part of the
interior drains away in the course of time, without affecting the
surfaces. If the thickness of the film is reduced by evaporation, its
tension may be either increased or diminished, according to the
relative volatility of its different components.
Let us now suppose that the thickness of the film is reduced until
the limit is reached at which the interior ceases to have the properties
of matter in mass. The elasticity of the film, which determines its
stability with respect to extension and contraction, does not vanish
at this limit. But a certain kind of instability will generally arise, in
virtue of which inequalities in the thickness of the film will tend to
increase through currents in the interior of the film. This probably
leads to the destruction of the film, in the case of most liquids. In
a film of soap-water, the kind of instability described seems to be
manifested in the breaking out of the black spots. But the sudden
diminution in thickness which takes place in parts of the film is
arrested by some unknown cause, possibly by viscous or gelatinous
properties, so that the rupture of the film does not necessarily follow.
Electromotive force. — The conditions of equilibrium may be modified
by electromotive force. Of such cases a galvanic or electrolytic cell
may be regarded as the type. With respect to the potentials for the
ions and the electrical potential the following relation may be noticed: —
When all the conditions of equilibrium are fulfilled in a galvanic
or electrolytic cell, the electromotive force is equal to the difference in
the values of the potential for any ion at the surfaces of the electrodes
multiplied by the electro-chemical equivalent of that ion, the greater
potential of an anion being at the same electrode as the greater elec-
trical potential, and the reverse being true of a cation.
The relation which exists between the electromotive force of a
perfect electro-chemical apparatus (i.e., a galvanic or electrolytic cell
which satisfies the condition of reversibility), and the changes in the
cell which accompany the passage of electricity, may be expressed by
the equation
d€ = (T-Tf)de+tdri + dWG+dWP, (30)
in which de denotes the increment of the intrinsic energy in the
apparatus, dq the increment of entropy, de the quantity of electricity
which passes through it, V and V" the electrical potentials in pieces
of the same kind of metal connected with the anode and cathode
respectively, dWQ the work done by gravity, and dWP the work done
by the pressures which act on the external surface of the apparatus.
The term dWQ may generally be neglected. The same is true of dWP,
when gases are not concerned. If no heat is supplied or withdrawn
ABSTRACT BY THE AUTHOR. 371
the term tdq will vanish. But in the calculation of electromotive
forces, which is the most important application of the equation, it is
convenient and customary to suppose that the temperature is main-
tained constant. Now this term tdr\, which represents the heat
absorbed by the cell, is frequently neglected in the consideration of
cells of which the temperature is supposed to remain constant. In
other words, it is frequently assumed that neither heat or cold is
produced by the passage of an electrical current through a perfect
electro-chemical apparatus (except that heat which may be indefinitely
diminished by increasing the time in which a given quantity of
electricity passes), unless it be by processes of a secondary nature,
which are not immediately or necessarily connected with the process
of electrolysis.
That this assumption is incorrect is shown by the electromotive
force of a gas battery charged with hydrogen and nitrogen, by the
currents caused by differences in the concentration of the electrolyte,
by electrodes of zinc and mercury in a solution of sulphate of zinc, by
a priori considerations based on the phenomena exhibited in the
direct combination of the elements of water or of hydrochloric acid,
by the absorption of heat which M. Favre has in many cases observed
in a galvanic or electrolytic cell, and by the fact that the solid or
liquid state of an electrode (at its temperature of fusion) does not
affect the electromotive force.
V.
ON THE VAPOR-DENSITIES OF PEROXIDE OF NITROGEN,
FORMIC ACID, ACETIC ACID, AND PERCHLORIDE OF
PHOSPHORUS.
[American Journal of Science, ser. 3, vol. xvm, Oct.-Nov. 1879.]
THE relation between temperature, pressure, and volume, for the
vapor of each of these substances differs widely from that expressed
by the usual laws for the gaseous state, — the laws known most
widely by the names of Mariotte, Gay-Lussac, and Avogadro. The
density of each vapor, in the sense in which the term is usually
employed in chemical treatises, i.e., its density taken relatively to
air of the same temperature and pressure,* has not a constant value,
but varies nearly in the ratio of one to two. And these variations
are exhibited at pressures not exceeding that of the atmosphere
and at temperatures comprised between zero and 200° or 300° of
the centigrade scale.
Such anomalies have been explained by the supposition that the
vapor consists of a mixture of two or three different kinds of gas
or vapor, which have different densities. Thus it is supposed that
the vapor of peroxide of nitrogen is a gas-mixture, the components
of which are represented (in the newer chemical notation) by N02
and N2O4 respectively. The densities corresponding to these formulae
are 1*589 and 3* 178. The density of the mixture should have a
value intermediate between these numbers, which is substantially
the case with the actual vapor. The case is similar with respect
to the vapor of formic acid, which we may regard as a mixture of
CH2O2 (density T589) and C2H4O4 (density 3178), and the vapor
of acetic acid, which we may regard as a mixture of C2H4O2
(density 2'073) and C4H8O4 (density 4146). In the case of per-
chloride of phosphorus, we must suppose the vapor to consist of
three parts; PC16 (the proper perchloride, density 7'20), PC13 (the
protochloride, density 4'98), and C12 (chlorine, density 2'22). Since
the chlorine and protochloride arise from the decomposition of the
perchloride, there must be as many molecules of the type C12 as of
the type PC18. Now a gas-mixture containing an equal number
* The language of this paper will be conformed to this usage.
VAPOR-DENSITIES. 373
of molecules of PC13 and C12 will have the density i(4'98 + 2'22)
or 3*60. It follows that, at least so far as the range of the possible
values of its density is concerned, we may regard the vapor as a
mixture in variable proportions of two kinds of gas having the
densities 7*20 and 3'60 respectively. The observed values of the
density accord with this supposition.
These hypotheses respecting the constitution of the vapors are
corroborated, in the case of peroxide of nitrogen and perchloride
of phosphorus, by other circumstances. The varying color of the
first vapor may be accounted for by supposing that the molecules
of the type N204 are colorless, while each molecule of the type NO2
has a constant color. This supposition affords a simple relation
between the density of the vapor and the depth of its color, which
has been verified by experiment.*
The vapor of the perchloride of phosphorus shows with increasing
temperature in an increasing degree the characteristic color of
chlorine. The amount of the color appears to be such as is required
by the hypothesis respecting the constitution of the vapor on the
very probable supposition that the perchloride proper is colorless,
but the case hardly admits of such exact numerical determinations
as are possible with respect to the peroxide of nitrogen.! But since
the products of dissociation are in this case dissimilar, they may be
partially separated by diffusion through a neutral gas, the lighter
chlorine diffusing more rapidly than the heavier protochloride.
The fact of dissociation has in this way been proved by direct
experiment. |
In the case of acetic and formic acids, we have no other evidence
than the variations of the densities in support of the hypothesis of
the compound nature of the vapor, yet if these variations shall
appear to follow the same law as those of the peroxide of nitrogen
and the perchloride of phosphorus, it will be difficult to refer them
to a different cause.
But however it may be with these acids, the peroxide of nitrogen
and the perchloride of phosphorus evidently furnish us with the
means of studying the laws of chemical equilibrium in gas-mixtures
in which chemical change is possible and does in fact take place
reversibly, with varying conditions of temperature and pressure.
Or, if from any considerations we can deduce a general law
* Salet, " Sur la coloration du peroxyde d'azote," Comptes Eendus, t. Ixvii, p. 488.
fH. Sainte-Claire Deville, "Sur les densites de vapeur," Comptea Rendus, t. Ixii,
p. 1157.
jWanklyn and Robinson, "On Diffusion of Vapours: a means of distinguishing
between apparent and real Vapour-densities of Chemical Compounds," Proc. Hoy. Soc.,
vol. xii, p. 507.
374 VAPOR-DENSITIES.
determining the proportions of the component gases necessary for
the equilibrium of such a mixture under any given conditions,
these substances afford an appropriate test for such a law.
In a former paper* by the present writer, equations were proposed
to express the relation between the temperature, the pressure or the
volume, and the quantities of the components in such a gas-mixture
as we are considering — a gas-mixtwe of convertible components in
the language of that paper. Applied to the vapor of the peroxide
of nitrogen, these equations led to a formula giving the density in
terms of the temperature and pressure, which was shown to agree
very closely with the experiments of Deville and Troost, and much
less closely, but apparently within the limits of possible error, with
the experiments of Playfair and Wanklyn. Since the publication
of that paper, new determinations of the density have been published
in different quarters, which render it possible to compare the equation
with the results of experiment throughout a wider range of tem-
perature and pressure. In the present paper, all experimental
determinations of the density of this vapor which have come to
the knowledge of the writer are cited, and compared with the values
demanded by the formula, and a similar comparison of theory and
experiment is made with respect to each of the other substances
which have been mentioned.
The considerations from which these formulae were deduced may
be briefly stated as follows. It will be observed that they are based
rather upon an extension of generally acknowledged principles to a
new class of cases than upon the introduction of any new principle.
The energy of a gas-mixture may be represented by an expression
of the form
j + Ej) + m2(c2t + E2) + etc.,
with as many terms as there are different kinds of gas in the mixture,
774, m2, etc. denoting the quantities (by weight) of the several com-
ponent gases, clt c2, etc., their several specific heats at constant volume,
Ej, Ej, etc., other constants, and t the absolute temperature. In like
manner the entropy of the gas-mixture is expressed by
t - C&! logN -^ J + m2(^H2 + c2 logN t-a2 logN — ) + etc.,
where v denotes the volume, and H^ a1? H2, a2, etc. denote constants
relating to the component gases, av a2, etc. being inversely pro-
portional to their several densities. The logarithms are Naperian.
"On the Equilibrium of Heterogeneous Substances," this volume, page 55. The
equations referred to are (313), (317), (319), and (320), on pages 171 and 172. The
applicability of these equations to such cases as we are now considering is discussed
under the heading "Gas-mixtures with Convertible Components," page 172.
VAPOR-DENSITIES. 375
These expressions for energy and entropy will undoubtedly apply
to mixtures of different gases, whatever their chemical relations may
be (with such limitations and with such a degree of approximation
as belong to other laws of the gaseous state), when no chemical action
can take place under the conditions considered. If we assume that
they will apply to such cases as we are now considering, although
chemical action is possible, and suppose the equilibrium of the mixture
with respect to chemical change to be determined by the condition
that its entropy has the greatest value consistent with its energy and
its volume, we may easily obtain an equation between ra^ m2, etc.,
t and v.*
The condition that the energy does not vary, gives
(m^ + w2c2 + etc.) dt + (cj -f- Ej) dm1 + (c2t + E2) dm2 + etc. = 0. (1 )
The condition that the entropy is a maximum implies that its
variation vanishes, when the energy and volume are constant.
This gives
logN t - a2 logN 2 dm2 + etc. = 0. (2)
Eliminating dt, we have
! - a, - G! - y + c, logN t - ^ logN
2 — a2 — c2 — ^+c2logN£ — a2logN— Jdm2+etc. = 0. (3)
If the case is like that of the peroxide of nitrogen, this equation
will have two terms, of which the second may refer to the denser
component of the gas-mixture. We shall then have a1 = 2a2, and
^ —dm2, and the equation will reduce to the form
1 mZV A
log = ~A-
where common logarithms have been substituted for Naperian, and
A, B and C are constants. If in place of the quantities of the
components we introduce the partial pressures, plt p2, due to these
components and measured in millimeters of mercury, by means of
the relations
P-.V
f-^
-7,
fat
*For certain a priori considerations which give a degree of probability to these
assumptions, the reader is referred to the paper already cited.
376 VAPOR-DENSITIES.
where c^ denotes a constant, we have
Pi
(5)
where A' and B' are new constants. Now if we denote by p the total
pressure of the gas-mixture (in millimeters of mercury), by D its
density (relative to air of the same temperature and pressure), and by
D! the theoretical density of the rarer component, we shall have
p-.p+p^.-.D^D.
This appears from the consideration that p+p2 represents what the
pressure would become, if without change of temperature or volume
all the matter in the gas-mixture could take the form of the rarer
component. Hence,
2D,-D
Pi=P-P2=P— fr-->
^i
p, D^D-D,)
^"p^-D)8'
By substitution in (5) we obtain
(6)
By this formula, when the values of the constants are determined, we
may calculate the density of the gas-mixture from its temperature
and pressure. The value of Dx may be obtained from the molecular
formula of the rarer component. If we compare equations (3), (4)
and (5), we see that
B' =
Now c1 — c2 is the difference of the specific heats at constant volume of
N02 and N2O4. The general rule that the specific heat of a gas at
constant volume and per unit of weight is independent of its conden-
sation, would make C^ — G^ B = 0, and B' = l. It may easily be shown,
with respect to any of the substances considered in this paper,* that
unless the numerical value of B' greatly exceeds unity, the term B'logi
may be neglected without serious error, if its omission is compensated
in the values given to A' and C. We may therefore cancel this term,
and then determine the remaining constants by comparison of the
formula with the results of experiment.
* For the case of peroxide of nitrogen, see pp. 180, 181 in the paper cited above.
VAPOE-DENSITIES. 377
In the case of a mixture of C12, PC13 and PC15, equation (3) will
have three terms distinguished by different suffixes. To fix our ideas,
we may make these suffixes 2, 3 and 5, referring to C12, PC13 and PC15
respectively. Since the constants a2, as and a5 are inversely propor-
tional to the densities of these gases,
and we may substitute — , — , - - for dm*,, cZm8 and dms in equation (3),
az as as
which is thus reduced to the form
log mL = _ A_B logj + C (7)
&m2m3 t
If we eliminate m2, m3, m6 by means of the partial pressures Pvp$,p6,
we obtain
when A', B', like A, B and C, are constants. If the chlorine and the
protochloride are in such proportions as arise from the decomposition
of the perchloride, pz=p3 and 4£>2£>3 = (p2+£>3)2. In this case, there-
fore, we have
It will be seen that this equation is of the same form as equation (5),
when p5 in (9) is regarded as corresponding to p2 in (5), and p2+pB in
(9), which represents the pressure due to the products of decomposition,
is regarded as corresponding to pl in (5), which has the same signifi-
cation. It follows that equation (5), as well as (6), which is derived
from it, may be regarded as applying to the vapor of perchloride of
phosphorus, when the values of the constants are properly determined.
This result might have been anticipated, but the longer course which
we have taken has given us the more general equations, (7) and (8),
which will apply to cases in which there is an excess of chlorine or
of the protochloride.
If the gas-mixture considered, in addition to the components
capable of chemical action, contains a neutral gas, the expressions for
the energy and entropy of the gas-mixture should properly each
contain a term relating to this neutral gas. This would make it
C 7YL
necessary to add cnmn to the coefficient of dt in (1), and n n to the
c
coefficient of dt in (2), the suffix n being used to mark the quantities
relating to the neutral gas. But these quantities would disappear
with the elimination of dt, and equation (3) and all the subsequent
equations would require no modification, if only p and D are estimated
(in accordance with usage) with exclusion of the pressure and weight
37S
VAPOR-DENSITIES.
due to the neutral gas. This result, which may be extended to any
number of neutral gases, is simply an expression of Dalton's Law.
We now proceed to the comparison of the formulae, especially of
equation (6), with the results of experiment.
TABLE I. — PEROXIDE OF NITROGEN.
Experiments at Atmospheric Pressure.
MlTSCHERLICH, — R. MtJLLER, — DEVILLE and TROOST.
Tempera-
ture.
Pressure.
Density
calculated
by eq. (10).
Density observed.
Deville & Troost.
Excess of observed density.
Deville & Troost.
Mb A
M— r. I. II.
in.
M— r. I.
II. ill. "
183-2
(760)
1-592
1-57
-•022
164-0
(760)
1-597
1-58
-•017
151-8
(760)
1-598
1-50
-•10
135-0
(760)
1-607
1-60
-•007
121-8
(760)
1-622
1-64
+ •02
121-5
(760)
1-622
1-62
-•002
111-3
(760)
1-641
1-65
+ •009
100-25
760
1-677
1-72
+ •04
100-1
(760)
1-676
1-68
+ •004
100-0
(760)
1-677
1-71
+ •03
90-0
(760)
1-728
1-72
-•008
84-4
(760)
1-768
1-83
+ •06
80-6
(760)
1-801
1-80
-•001
79
748
1-814
1-84
+ •03
77-4
(760)
1-833
1-85
+ •02
70-0
(760)
1-920
1-92
•000
70
754-5
1-919
1-95
+ •03
68-8
(760)
1-937
1-99
+ •05
66-0
(760)
1-976
2-03
+ •05
60-2
(760)
2-067
2-08
+ •013
55-0
(760)
2-157
2-20
+ •04
52
757
2-211
2-26
+ •05
49-7
(760)
2-255
2-34
+ •09
4
49-6
(760)
2-256
2-27
+ •014
45-1
(760)
2-342
2-40
+ •06
39-8
(760)
2-443
2-46
+ •017
35-4
(760)
2-524
2-53
+ •006
35-2
(760)
2-528
2-66
+ •13
34-6
(760)
2-539
2-62
+ •08
32
748
2-582
2-65
+ •07
28-7
(760)
2-642
2-80
+ •16
28
751
2-652
2-70
+ •05
27-6
(760)
2-661
2-70
+ •04
26-7
(760)
2-676
2-65
-•026
Peroxide of nitrogen. — If we take the constants of the equation for
this substance from the paper already cited,* we have
15-89(D- 1-589) 3118-6
log (3-178-DV* ; 27q+logff-12-451, (10)
\O JL I O ^^ U 'I l/Q ~j~ & i O
tc denoting the temperature on the centigrade scale. The numbers
3-178 and 1*589 represent the theoretical densities of N2O4 and NO2
*8ae equation (336) on page 177,— also the following equations in which the density
b given in terms of the temperature and pressure. In comparing these equations, it
must be observed that in (336) the pressures are measured in atmospheres, but in this
paper in millimeters of mercury.
VAPOK-DENSITIES. 379
respectively. The two other constants were determined by the
experiments of Deville and Troost.
The results of these and other experiments at atmospheric pressure,
all made by Dumas' method, are exhibited in Table I. The first three
columns give the temperature (centigrade), the pressure (in millimeters
of mercury),* and the density calculated from the temperature and
pressure by equation (10). The subsequent columns give the densities
observed by different authorities, and the excess of the observed over
the calculated densities. In the first column of observed densities,
we have one observation by Mitscherlich t (at 100*25°) and five by
R. Mliller. J The three remaining columns contain each the results of
a series of experiments by Deville and Troost. § In each series the
experiments were made with increasing temperatures, and with the
same vessel, without refilling. It should be observed that the results
of the three series are not regarded by their distinguished authors as
of equal weight. It is expressly stated that the numbers in the two
earlier series, and especially in the first, may be less exact. The last
series agrees very closely with the formula. It was from this that
the constants of the formula were determined. The experiments of
series I and II, and those of Mitscherlich and Muller, give somewhat
larger values, with a single exception, as is best seen in the columns
which give the excess of the observed density. The differences be-
tween the different columns are far too regular to be attributed to
the accidental errors of the individual observations, except in the
case of the experiment at 151 '8°, where some accident has evidently
occurred either in the experiment itself or in the reduction of the
result. Setting this observation aside, we must look for some constant
cause for the other discrepancies between the different series.
We can hardly attribute these discrepancies to difference in the
material employed, or to air or other foreign substance imperfectly
expelled from the flask. For impurities which increase the density
would make the divergence between the different series greatest
when the densities are the least, whereas the divergences seem to
vanish as the density approaches the limiting value. (A similar
* TOO"1111 has been assumed as the pressure of the atmosphere in all cases in which the
precise pressure is not recorded in the published account of the experiments. The
figures inserted in the columns of pressures are in such cases enclosed in parentheses.
The same course has been followed in the subsequent tables. With respect to the
principal series of observations by Deville and Troost (series III), it is stated that the
barometer varied between 747 and 764 millimeters. A difference of 13 millimeters in
the pressure would in no case cause a difference of '005 in the calculated densities. In
this series, therefore, the errors due to this circumstance are not very serious.
•\Pogg. Ann., vol. xxix (1833), p. 220.
| Lieb. Ann., vol. cxxii (1862), p. 15.
§ Comptes Rendus, vol. Ixiv (1867), p. 237.
380 VAPOR-DENSITIES.
objection would apply to the supposition of any error in the deter-
mination of the weight of the flask when filled with air alone.)
But if we should attribute the divergences to an impurity which
diminishes the density (as air), we should be driven to the conclusion
that the first series of Deville and Troost gives the most correct
results, and that all the best attested numbers at temperatures
below 90° are considerably in the wrong. It does not seem possible
to account for these discrepancies by any causes which would apply
to cases of normal or constant density. They are illustrations of
the general fact that when the density varies rapidly with the
temperature, determinations of density for the same temperature
and pressure by different observers, or different determinations by
the same observer, exhibit discordances which are entirely of a
different order of magnitude from those which occur with substances
of normal or constant densities, or which occur with the same
substance at temperatures at which the density approaches a
constant value. In some cases such results may be accounted for
by carelessness on the part of the observers, not controlled by a
comparison of the result with a value already known. But such an
explanation is inadequate to explain the general fact, and evidently
inadmissible in the present case.
It is probable that these discrepancies are in part attributable
to a circumstance which has been noticed by M. Wurtz, in his
account of his experiments upon the vapor-density of bromhydrate
of amylene, in the following words : — " Le temps pendant lequel la
vapeur est maintenue a la temperature ou Ton determine la densite
n'est pas sans influence sur les nombres obtenus. C'est ce qui result
des deux experiences faites a 225 degrees avec des produits identiques.
Dans la premiere, la vapeur a ete portee rapidement a 225 degre's.
Dans la seconde elle a ete maintenue pendant dix minutes a cette
temperature. On voit que les nombres trouves pour les densites ont
e'te fort difieYents. (The numbers were 4*69 and 3*68 respectively.)
Ce resultat ne doit point surprendre si Ton considere que le pheno-
mene de decomposition de la vapeur doit absorber de la chaleur, et
que les quantity's de chaleur necessaires pour produire et la dilatation
et la decomposition ne sauraient etre fournies instantanement."*
It is not difficult to form an estimate of the quantities of heat
which come into play in such cases. With respect to peroxide of
nitrogen, it was estimated in the paper already cited that the heat
absorbed in the conversion of a unit of N204 into NO2 under
constant pressure is represented by 7181 a2. (The heat is supposed
to be measured in units of mechanical work.) Now the external
* Comptes Rendua, t. Ix, p. 730.
VAPOR-DENSITIES. 381
work done by the conversion of a unit of N204 into N02 under
constant pressure is a2t. Therefore, the ratio of the heat absorbed
to the external work done by the conversion of N204 into NO2 is
7l81-i-£, or 23 at the temperature of 40° centigrade. Let us next
consider how much more rapidly this vapor expands with increase
of temperature at constant pressure than air. From the necessary
relation
kmt
v = ^r\>
pD
where m denotes the weight of the vapor, and k a constant, we obtain
(dv\ _v__v^(dG\
\dt)p~t BVcEf/,'
where the suffix p indicates that the differential coefficients are for
constant pressure. The last term of this expression evidently denotes
the part of the expansion which is due to the conversion of N2O4
into NO2, and the preceding term the expansion which would take
place if there were no such conversion, and which is identical with
the expansion of the same volume of air under the same circum-
stances. The ratio of the two terms is — T^l^rr ) , the numerical
D \ at /p
value of which for the temperature of 40° is 2 '42, as may be found
by differentiating equation (10), or, with less precision, from the
numbers in the third column of Table I. Let us now suppose that
equal volumes of peroxide of nitrogen and of air at the temperature
of 40° and the pressure of one atmosphere receive equal infinitesimal
increments of temperature under constant pressure. The heat ab-
sorbed by the peroxide of nitrogen on account of the conversion of
N2O4 into NO2 is 23 times the external work due to the same cause,
and this work is 2'42 times the external work done by the expansion
of the air. But the heat absorbed by the air in expanding under
constant pressure is well known to be 3'5 times the work done.
Therefore the heat absorbed on account of the conversion of N2O4
into NO2 is (23 X 2*42 -7- 3*5 = ) 15'9 times the heat absorbed by the air.
To obtain the whole heat absorbed by the vapor we must add that
which would be required if no conversion took place. At 40° the
vapor of peroxide of nitrogen contains about 54 molecules of N2O4
to 46 of NO2, as may easily be calculated from its density. The
specific heat for constant pressure of a mixture in such proportions
of gases of such molecular formulae, if no chemical action could take
place, would be about twice that of the same volume of air. Adding
this to the heat absorbed by the chemical action we obtain the final
result, — that at 40° and the pressure of the atmosphere the specific
382 VAPOR-DENSITIES.
heat of peroxide of nitrogen at constant pressure is about eighteen
times that of the same volume of air.*
But the greater amount of heat which is required to bring the
vapor to the desired temperature is only one factor in the increased
liability to error in cases of this kind. The expansion of peroxide
of nitrogen for increase of temperature under constant pressure at
40° is 3'42 times that of air. If, then, in a determination of density,
the vapor fails to reach the temperature of the bath, the error due
to the difference of the temperature of the vapor and the bath, will
be 3*42 times as great as would be caused by the same difference
of temperatures in the case of any vapor or gas having a constant
density. When we consider that we are liable not only to the same,
but to a much greater difference of temperatures in a case like that
of peroxide of nitrogen, when the exposure to the heat is of the same
duration, it is evident that the common test of the exactness of a
process for the determination of vapor-densities, by applying it to
a case in which the density is nearly constant, is entirely insufficient.
That the experiments of the IIId series of Deville and Troost give
numbers so regular and so much lower than the other experiments
is probably to be attributed in part to the length of time of exposure
to the heat of the experiment, which was half an hour in this series, —
for the other series, the time is not given.
Another point should be considered in this connection. During
the heating of the vapor in the bath, it is not immaterial whether
the flask is open or closed. This will appear, if we compare the
values of f -^-J and (-53 )» the differential coefficients of the density
with respect to the temperature on the suppositions, respectively, of
constant pressure, and of constant volume. For 40°, we have
= •0163,
i
the first number being obtained immediately from equation (10) by
differentiation, and the second by differentiation after substitution
/' in f
of — |x- for p. The ratio of these numbers evidently gives the
proportion in which the chemical change takes place under the two
suppositions. This shows that only about six-sevenths of the heat
required for the chemical change can be supplied before opening
the flask, and the remainder of this heat as well as that required
for expansion must be supplied after the opening. The errors due
* Similar calculations from less precise data for the bromhydrate of amylene at 225°
seem to indicate a specific heat as much as forty times as great as that of the same
volume of air.
VAPOR-DENSITIES. 383
to this source may evidently be diminished by diminishing the
intervals of temperature between the successive experiments in a
series of this kind, and also by diminishing the opening made in
the flask, which increases the time for which the flask may be left
open without danger of the entrance of air. In the IIId series of
experiments by Deville and Troost, the intervals of temperature did
not exceed ten degrees (except after the density had nearly reached
its limiting value), and the necit of the flask was drawn out into a
very fine tube.
In Table II, which relates to experiments on the same substance
at pressures less than that of the atmosphere, the principal series
is that of Naumann,* which commences a few degrees below the
lowest temperatures of Deville and Troost, and extends to —6°
centigrade, the pressures varying from 301 to 84 millimeters. These
experiments were made by the method of Gay-Lussac. The numbers
in the column of observed densities have been re-calculated from
the more immediate results of the experiments, and are not in all
cases identical with those given in Professor Naumann's paper.
Every case of difference is marked with brackets. Instead of the
numbers [2'66], [2'62], [2*85], [2*94], Naumann's paper has 2'57, 2*65,
2*84, 3*01, respectively. In some cases the temperatures and pressures
of two experiments are so nearly the same that it would be allowable
to average the results, at least in the column of excess of observed
density. In such cases the numbers in this column have been
united by a brace. The greatest difference between the observed
and calculated densities is *16, which occurs at the least pressure,
84 millimeters. In this experiment the weight of the substance
employed is also less than in any other experiment. Under such
circumstances, the liability to error is of course greatly increased.
The average difference between the observed and calculated densities
is '063. Since these differences are almost uniformly positive and
increase as the temperature diminishes, it is evident that they might
be considerably diminished by slight changes in the constants of
equation (10), without seriously impairing the agreement of that
equation with the experiments of Deville and Troost. But it has
not seemed necessary to re-calculate the formula, which, in its present
form, will at least illustrate the degree of accuracy with which
densities at low pressures and at temperatures below the boiling
point of the liquid may be derived from experiments at atmospheric
pressure above the boiling point. Moreover, the excess of observed
density may be due in part to a circumstance mentioned by Professor
Naumann, that the chemical action between the vapor and the
Berichte der deutschen chemischen Gesellschaft, Jahrgang xi (1878), S. 2045.
384
VAPOR-DENSITIES.
mercury diminished the volume of the vapor, and thus increased
the numbers obtained for the density.
TABLE II. — PEROXIDE OF NITROGEN.
Experiments at less than Atmospheric Pressure.
PLAYFAIB AND WANKLYN, — TROOST,— NAUMANN.
Tempera-
ture.
Pressure.
Density
calculated
by eq. (10).
Density observed.
P. & W. T. N.
Excess of obs. density.
P. & W. T. N.
97-5
(301)
1-631
1-783
+ •152
27
35
1-90
1-6
-•30
27
16
1-77
1-59
-•18
24-5
(323)
2-524
2-52
-•004
22-5
136-5
2-34
2-35
+ •01
22-5
101
2-26
2-28
+ •02
21-5
161
2-41
2-38
-•03\
20-8
153-5
2-41
2-46
+ -05/
20
301
2-59
2-70
+ •11
18-5
136
2-43
2-45
+ •02
18
279
2-61
2-71
+ •10
17'5
172
2-51
2-52
+ -oi\
16-8
172
2-53
2-55
+ -02J
16-5
224
2-59
[2-66]
+ -07\
16
228-5
2-61
[2-62]
+ -01/
14-5
175
2-58
2-63
+ •05
11-3
(159)
2-620
2-645
+ •025
11
190
2-66
2-76
+ •10
10-5
163
2-64
2-73
+ •09
4-2
(129)
2-710
2-588
-•122
4
172-5
2-77
2-85
+ •08
2-5
145
2-76
[2-85]
+ •09
1
138
2-78
2-84
+ •06
-1
153
2-83
2-87
+ •04
-3
84
2-76
2-92
+,•16
-5
123
2-85
2-98
+ '13\
-6
125-5
2-87
[2-94]
+ -07J
The same table includes two experiments of Troost,* by Dumas*
method, but at the very low pressures of 35mm and 16mm. In such
experiments we cannot expect a close agreement with the formula,
for the same error in the determination of the weight of the vapor,
which would make a difference of '01 in the density in experiments
at atmospheric pressure, would make a difference of '21 or '47 in the
circumstances of these experiments. In fact, the numbers obtained
differ considerably from those demanded by the formula.
There remain four experiments by Play fair and Wanklynt in
which Dumas' method was varied by diluting the vapor with
nitrogen. The numbers in the column of pressures represent the
total pressure diminished by the pressure which the nitrogen alone
would have exerted. They are not quite accurate, since the data
given in the memoir cited only enable us to determine the ratios
* Compte* Rtndus, t. Ixxxvi (1878), p. 1395.
t Trant. Roy. Soc. Edinb., vol. xxii (1861), p. 463.
VAPOR-DENSITIES. 385
of the total and the partial pressures. The numbers here given
are obtained by setting the total pressure, which was that of the
atmosphere at the time of the experiment, equal to 760mm. The
effect of this inaccuracy upon the calculated densities would be
small. Two of these observations agree closely with the formula;
and two show considerable divergence, but in opposite directions,
and these are the two in which the quantities of peroxide of nitrogen
were the smallest. The differences appear to be attributable rather
to the difficulty of a precise determination of the quantities of
nitrogen and of vapor, than to any effect of the one upon the
other.
Special interest attaches to experiments at the same or nearly the
same temperature but different pressures. For with experiments at
the same temperature, the constants of the formula which are deter-
mined by observation are reduced to one, so that the verification of
the formula by experiment cannot possibly be regarded as a case
of interpolation. It is not necessary that the temperatures should
be exactly the same, for it will be conceded that the formula
represents the actual function well enough to answer for adjusting
slight differences of temperature ; but it is necessary that the
range of pressures should be considerable in order that the differ-
ences of density should be large in proportion to the probable
errors of observation. But the pressures must not be so low that
accurate determinations become impossible.
In the experiments of Naumann we see some fair correspondences
with the formula in respect to the influence of pressure, especially
in the first four experiments of the list, where, if we average the
results of the third and fourth experiments, as is evidently allowable,
the observed values follow very closely the fluctuations of the cal-
culated, extending from 2*26 to 2*41. In other cases the agreement
is less satisfactory. The circumstance that the experiments at the
two highest pressures (301 and 279mm) give results exceeding the
calculated values considerably more than any other experiments at
adjacent temperatures may seem to indicate that the densities increase
with the pressures more rapidly than the formula allows; but the
differences are not too large to be ascribed to errors of observation,
and the experiment at the lowest pressure (84mm) also shows a large
excess of observed density.
A much more critical test may be found in the comparison of
Naumann's experiments with those of Deville and Troost, notwith-
standing the interval of about 4° of temperature. The formula
requires that a diminution of pressure from 760 to 101 millimeters
shall reduce the density from 2'676 at 26'7° to 2'26 at 22'5°, not-
withstanding the effect of the change of temperature. Experiment
G. i. 2 B
386 VAPOR-DENSITIES.
gives a reduction of density from 2*65 to 2*28, which is about one-
ninth less. This is, it will be observed, a deviation from the formula
in the opposite direction from that which the experiments of Naumann
alone, or a comparison of the experiments of Troost with those of
Deville and Troost, seemed to indicate. The experiment here com-
pared with Naumann's belongs to the IIId series of Deville and Troost.
If instead of this experiment we should take an average of the
experiments at lowest temperature in the IId and IIId series, the
agreement with the formula with respect to the effect of change of
pressure would be almost perfect.
Formic acid. — In Table III, the determinations of Bineau are
compared with the densities calculated by the formula
1-589 (D- 1-589) 3800
lQg (8178-Dy =MT273+1°^-12'64L (11)
The observed densities are taken from the eighteenth volume of
the third series of the Annales de Chimie et de Physique (1846),
except in three cases, distinguished by parentheses, which are earlier
determinations published in the nineteenth volume of the Comptes
Rendus (1844). It may be added that the pressure (687) for the
experiment at 108° is taken from Erdmann's Journal fur praktische
Chemie (vol. xl, p. 44), the impression being imperfect in the Annales,
in the copies to which the writer has been able to refer, where the
figures look much like 637. (The pressure 637 would make the
calculated density 2*28.)
In the column which gives the excess of observed densities, the
effect of nearness to the state of saturation is often very marked.
Such cases are distinguished by an asterisk. The temperature of
99*5° is below the boiling point of formic acid, and the higher
pressures employed at this temperature cannot be far from the
pressure of saturated vapor. With respect to lower temperatures,
we have the statement of Bineau that the pressure of saturated
vapor is about 19mm at 13°, 20'5mm at 15°, 33'5mm at 22°, and 53'5mm
at 32°. By interpolation between the logarithms of these pressures
(in a single case, by extrapolation), we obtain the following result : —
Temperature, - 10 '5 12 '5 16 18 '5 22
Pressure of sat. vapor, - 16 "6 18 '5 22 26 '2 33 "5
Pressure of experiment, - 14 '69 15 '20 15 '97 23 '53 25 '17
VAPOR-DENSITIES.
387
TABLE III. — FORMIC ACID.
EXPERIMENTS OF BINEAU.
Temperature.
Pressure.
Density
calculated by
eq. (11X
Density
observed.
Excess
of observed
density.
216-0
690
1-60
1-61
+ •01
184-0
750
1-64
1-68
+ •04
125-5
687
2-03
2-05
+ •02
125-5
645
2-02
2-03
+ •01
124-5
670
2-04
2-06
+ •02
124-5
640
2-03
2-04
+ •01
118-0
655
2-13
(2-14)
( + •01)
118-0
650
2-13
2-13
•00
117-5
688
2-15
2-13
-•02
115-5
649
2-17
2-20
+ •03
115-5
640
2-16
2-16
•00
115
655
2-18
(2-13)
(-•05)
111-5
690
2-25
2-22
-•03
111-5
690
2-25
2-25
•00
111
608
2-22
(2-13)
(-•09)
108
[687]
2-30
2-31
+ •01
105-0
691
2-35
2-35
•00
105-0
650
2-34
2-33
-•01
105-0
630
2-33
2-32
-•01
101-0
693
2-42
2-44
+ •02
101-0
650
2-40
2-41
+ •01
99-5
690
2-44
2-52
+ •08*
99-5
684
2-44
2-49
+ •05
99-5
676
2-44
2-46
+ •02
99-5
662
2-43
2-44
+ •01
99-5
641
2-42
2-42
•00
99-5
619
2-41
2-41
•00
99-5
602
2-41
2-40
-•01
99-5
557
2-39
2-34
-•05
34-5
28-94
2-82
2-77
-•05
31-5
3-04
2-40
2-60
+ •20
30-5
8-83
2-67
2-69
+ •02
30-0
18-28
2-81
2-76
-•05
29-0
27-40
2-88
2-83
-•05
24-5
17-39
2-88
2-86
-•02
22-0
25-17
2-95
3-05
+ •10*
20-0
16-67
2-93
2-94
+ •01
20-0
7-99
2-84
2-85
+ •01
20-0
2-72
2-64
2-80
+ •16
18-5
23-53
2-98
3-23
+ •25*
16-0
15-97
2-97
3-13
+ •16*
15-5
2-61
2-72
2-86
+ •14
15-0
7-60
2-90
2-93
+ •03
12-5
15-20
3-00
3-14
+ •14*
11-0
7-26
2-95
3-02
+ •07
10-5
14-69
3-01
3-23
+ •22*
Whether the large excess of observed density in these cases represents
a property of the vapor, or an incipient condensation on the walls
of the vessel which contains it, as has been supposed by eminent
physicists in similar cases, we need not here discuss.
If we reject these cases of nearly saturated vapor, as well as the
three earlier determinations, there remain 25 experiments at pressures
somewhat less than one atmosphere in which the maximum difference
388 VAPOR-DENSITIES.
between the observed and calculated densities is '05, and the average
difference '016; nine experiments at pressures ranging from 29mm
to 7min, in which the maximum difference is "07 and the average '035 ;
and three experiments at pressures of about 3mm, in which the average
difference is '17. The extraordinary precision of the determinations
at low pressures is doubtless due to the large scale on which the
experiments were conducted. All the experiments at temperatures
below 99° were made with a globe of the capacity of 5| liters with
a stem of suitable length to hold the barometric column.
The agreement is certainly as good as could be desired, and shows
the accuracy of which the method of observation is capable. But
in no part of the thermometric scale do we find so great a range
of pressures as might be desired, without using pressures too low
for accurate results, or observations which are to be rejected for
other reasons.
Acetic acid. — For this substance the densities have been calculated
by the formula
2-073(D- 2-073) 3520
(4-146-Dy "
the constants 3520 and 11 '349 being derived from the determinations
of Cahours and Bineau, which with those of Horstmann and Troost
are given in Table IV. The experiments of Cahours and Horstmann
were made under atmospheric pressure, those of Horstmann* by the
method of Bunsen, those of Cahours presumably by the method of
Dumas. The numbers in the first column of the densities observed
by Cahours are taken from the twentieth volume (1845) of the
Comptes Rendus, except a few cases, distinguished by parentheses,
which are taken from the preceding volume (1844). The numbers
in the second column are taken from his Lecons de chimie generate
Jlementaire, 1856. These numbers seem to be based in part upon
new experiments and in part upon a revision of the observations
recorded in the Comptes Rendus, the calculations being carried out
to another figure of decimals. They are therefore entitled to a
greater weight than the numbers of the preceding column.
The agreement of the formula with the numbers given in the
Lemons de chimie is very good, the greatest divergences being *080
at 190° and '062 at 180°. But at 190° the table in the Comptes
Rendus agrees precisely with the formula, and at 171° (the next
experiment) it shows a divergence in the opposite direction. The
next divergences in the order of magnitude are — '033, — '036, — '032
* Lieb. Ann., suppl. vi, p. 65.
VAPOR-DENSITIES.
389
TABLE IV. — ACETIC ACID.
EXPERIMENTS OF CAHOURS,— HORSTMANN,— BINBAU,— TROOST.
Tempera-
ture.
Pressure.
Density
calculated
byeq.(12).
Density observed.
Cahours.
Excess of observe
Cahours.
d density.
Horst-
mann.
C. R.
Lecona. mann.
C. R. Lec.008.
338
(760)
2-077
2-08
•00
336
(760)
2-077
2-082
+ •005
327
(760)
2-078
2-08
2-085
•00 +-007
321
(760)
2-079
2-08
2-083
•00 +-004
308
(760)
2-081
2-085
+ •004
300
(760)
2-082
2-08
•00
295
(760)
2-084
2-083
-•001
280
(760)
2-089
2-08
-•01
272
(760)
2-093
2-088
-•005
254-6
747-2
2-105
2-135
+ •030
252
(760)
2-108
2-090
-•018
250
(760)
2-111
2-08
-•03
240
(760)
2-122
2-090
-•032
233-5
752-8
2-132
2-195
+ •083
231
(760)
2-137
(2-12)
2-101
( - -02) - -036
230
(760)
2-139
2-09
-•05
219
(760)
2-165
2-17
2-132
+ -01 - -033
200
(760)
2-239
2-22
2-248
- -02 + -009
190
(760)
2-298
2-30
2-378
•00 +-080
181-7
749-7
2-359
2-419
+ •060
180
(760)
2-376
2-438
+ •062
171
(760)
2-466
2-42
-•05
170
(760)
2-477
2-480
+ •003
165-0
754-1
2-534
2-647
+ •113
162
(760)
2-575
2-583
+ •008
160-3
751-6
2-594
2-649
+ •055
160
(760)
2-601
2-48
-•12
152
(760)
2-716
(272)
2-727
(•00) +'011
150
(760)
2-747
2-75
•00
145
(760)
2-826
(2-75)
(-•08)
140
(760)
2-910
2-90
2-907
- -01 - -003
134-3
748-8
3-001
3-108
+ •107
131-3
754-1
3-055
3-070
+ •015
130
(760)
3-082
3-12
3-105
+ •04 +-023
128-6
752-9
3-103
3-079
-•024
125
(760)
3-168
3-20
+ •03
124
(760)
3-185
3-194
+ •009
Bineau.
Troost.
Bineau.
Troost
132
757
3-05
(2-86)
(-•19)
130
59-7
2-31
2-12
-•19
130
30-6
2-21
2-10
-•11
129
633
3-03
(2-88)
(-'15)
36-5
11-32
3-63
3-62
-•01
35-0
11-19
3-65
3-64
-•01
30-0
6-03
3-61
3-60
-•01
28-0
10-03
375
3-75
•00
24-0
5-75
3-71
3-70
-•01
22-0
8-64
3-82
3-85
+ •03
22
2-70
3-59
3-56
-•03
21-0
4-06
3-70
3-72
+ •02
20-5
10-03
3-86
3-95
+ •09
20-0
8-55
3-84
3-88
+ •04
20-0
5-56
3-77
3-77
•00
19-0
4-00
3-73
3-75
+ •02
19
2-60
3-65
3-66
+ •01
12-0
5-23
3-88
3-92
+ •04
12
2-44
3-77
3-80
+ •03
11-5
3-76
3-84
3-88
+ •04
390 VAPOK-DENSITIES.
at 219°, 231°, 240°, respectively. Here the table in the Gomptes
Rendiis agrees substantially with that of the Lepons, but the experi-
ments of Horstmann show a divergence in the opposite direction.
In fact, the three columns of observed densities nowhere agree in
the direction of their divergence from the formula.
The somewhat decided differences between the results of Horst-
mann and those of Cahours may be due in part to the different
methods of observation, especially to the entirely different manner
of applying the heat and measuring the temperature. But the higher
values obtained by Horstmann cannot be accounted for by too short
an exposure to the source of heat, for his experiments were made
with decreasing temperatures.
The determinations of Bineau are taken from the same sources as
those on formic acid, the earlier determinations being distinguished
as before by parentheses. One of these (at 132°) was made by the
method of Dumas, the other by that of Gay-Lussac. The smallness
of the observed densities appears due to the presence of water. (An
acidimetric test gave 295 parts of acid in 306.) The other experi-
ments were made with the same apparatus which was used with
formic acid and show even greater regularity in their results than
the experiments with that substance. Only in one case is the
influence of proximity to saturation seen, viz., at 20*5° and 10'03mm,
the pressure of saturated vapor at this temperature being about
12'7mm.* In the remaining fifteen observations of this series, not-
withstanding the very low pressures employed (from 2'44 to 11 "32),
the greatest difference between the observations and the formula
is "04, and the average difference *02.
The two observations by Troostt were made by the method of
Dumas, but at pressures very low for this method. The results
obtained differ considerably from the formula, but not so much as
in the case of his experiments at low pressure with peroxide of
nitrogen.
Table V contains the experiments of NaumannJ on acetic acid.
These consist of ten series (distinguished by the letters A, B, C, etc.)
of observations by Hoffmann's method. § The temperatures of the
observations in the different series are for the most part the same,
so that for each temperature we have observations through a wide
range of pressures. Within each compartment of the table are given
* This number is obtained from data given by Bineau by the same kind of interpola-
tion which was used for formic acid.
t Comptes Rendua, vol. Ixxxvi (1878), p. 1395.
% Lieb. Ann., vol. civ, p. 325.
§ This is a modification of the method of Gay-Lussac, in which the heat is supplied
by a vapor bath.
VAPOR-DENSITIES.
391
TABLE V. — ACETIC ACID.
EXPERIMENTS OF NAUMANN.
TEM
[PERATl
JRE.
78°
100°
110°
120°
130°
140°
160°
160°
185°
/'Pressure.
. 1 D. calc.
A1 D. obs.
I Exc. of D. obs.
393-5
3-39
3-44
+ •05
411
3-23
3-31
+ •08
432
3-06
3-14
+ •08
455
2-90
2-97
+ •07
477
2-75
2-82
+ •07
498*5
2-61
2-68
+ •07
565
2-28
2-38
+ •08
{Pressure.
D. calc.
D. obs.
Exc. of D. obs.
342-3
3-35
3-37
+ •02
359-3
3-18
3-22
+ •04
377-5
3-02
3-06
+ •04
398-5
2-85
2-89
+ •04
417-5
2-70
2-75
+ •05
436-5
2-57
2-63
+ •06
495
2-28
2-31
+ •05
( Pressure.
f^j D. calc.
^1 D. obs.
lExc. of D. obs.
258
3-26
3-17
-•09
382
2-22
2-25
+ •03
{Pressure.
D. calc.
D. obs.
Exc. of D. obs.
232
3-23
3-12
-•11
252
2-87
2-94
+ •07
274
2-72
2-68
-•04
287-5
2-58
2-54
-•04
300
2-46
2-44
-•02
335
2-21
2"-23
+ •02
{Pressure.
D. calc.
D. obs.
Exc. of D. obs.
164
3-53
3-41
-•12
186
3-15
3-06
-•09
197
2-97
2-91
-•06
209
2-81
2-75
-•06
221
2-65
2-61
-•04
232
2-52
2-50
-•02
243
2-41
2-40
-•01
253
2-32
2-31
-•01
269
2-18
2-22
+ •04
{Pressure.
D. calc.
D. obs.
Exc. of D. obs.
149
3-50
3-34
-•16
168
3-12
3-01
-•11
201
2-62
2-56
-•06
{Pressure.
D. calc.
D. obs.
Exc. of D. obs.
137
3-48
3-26
-•22
156
3-09
2-98
-•11
166-5
2-92
2-81
-•11
180
.2-75
2-61
-•14
188
2-60
2-50
-•10
199
2-47
2-40
-•07
208-2
2-37
2-29
-•08
230
2-17
2-14
-•03
{Pressure.
D. calc.
D. obs.
Exc. of D. obs.
113
3-42
3-25
-•17
130
3-03
2-94
-•09
138-5
2-85
2-78
-•07
149
2-69
2-60
-•09
157-5
2-55
2-47
-•08
168-2
2-43
2-32
-•11
175
2-33
2-26
-•07
191-5
2-15
2-13
-•02
C Pressure.
T I D. calc.
J)D. obs.
I Exc. of D. obs.
80
3-32
3-06
-•26
92
2-91
2-76
-•15
98-5
2-73
2-61
-•12
106
2-58
2-46
-•12
112-5
2-45
2-34
-•11
117'3
2-35
2-27
-•08
129-2
2-21
2-11
-•10
( Pressure.
vj D. calc.
T] D. obs.
I Exc. of D. obs.
66
3-26
3-04
-•22
77-7
2-85
2-66
-•19
84
2-68
2-49
-•19
89-5
2-53
2-37
-•16
93
2-40
2-32
-•08
98
2-31
224
-•07
103
2-24
2-16
-•08
110-5
2-12
2-11
-•01
in order the pressure of an experiment, the density calculated by
equation (12), the observed density, and the excess of observed density,
the temperature of the experiment being given at the head of the
column. These experiments, taken by themselves, seem to show an
effect of pressure upon the density about one third greater than is
indicated by the formula. But the divergences (of which the greatest
is '26 and the average '085) are not large in view of the fact that
the experiments were undertaken rather with the desire of obtaining
a great number of observations with moderate labor, than with the
intention of attaining the greatest possible accuracy.
392 VAPOR-DENSITIES.
The quantity of acid diminishes somewhat regularly from '2084
grams in series A to '0185 in series K. The volume, which was
154°° in the experiment at 185° in series A, diminishes in the
successive series, and in the same series with diminishing temperature,
to 69'6OC in the experiment at 78° in series K. It is worthy of notice
that the greatest deviations from the formula occur where the liability
to error is most serious with respect to pressure (which was measured
without a cathetometer), to volume, and to the quantity of acid.
Far more serious than the absolute amount of these divergences, is
the regularity which they exhibit. But it must be remembered that
the observations are by no means entirely independent, and many
sources of possible error, such as the calibration of the tube and the
determination of the quantity of acid, might affect the results with
considerable regularity.
Only to a slight degree can the divergences from the formula be
accounted for by an insufficient exposure to the temperature of the
experiment. The observations, except those at 78°, were made with
increasing temperatures, and the greatest divergences from the formula
are not in the positive direction. Yet the positive divergences occur
where we should most expect to find them, if they were due to this
cause, viz., in the series in which the greatest quantities of acid were
used, and in cases in which the temperature seems to have been
raised at once an unusual number of degrees. (See especially the
observation at 120° in series D, 'and in general the observations at
185°, which exhibit if not a positive at least a diminution of negative
excess.) In the observations at 78°, which were the last of each
series, and therefore followed a fall of temperature from 185°, we find
in some cases, especially in series G, H, and J, a negative divergence
much greater than in the other determinations of the same series, and
which appears to be referable to this circumstance.
In Table VI are exhibited the results of experiments by Playfair
and Wanklyn,* in which the vapor of the acid was diluted with
hydrogen or, in a single case (the experiment at 95'5°), by air.
Columns I and II of the observed densities relate each to a series of
observations by the method of Gay-Lussac, column III contains four
independent determinations by the method of Dumas. The numbers
in the column of pressures are, as in other similar cases, the partial
pressures obtained by subtracting from the total pressure (which was
never very much less than that of the atmosphere) that which would
be exerted by the hydrogen or air alone.
The first observation of the first series gives the density T936,
which is doubtless too small, since it is much less than the theoretical
* Trans. Roy. Soc. Edirib., vol. xxii, p. 455.
VAPOR-DENSITIES.
limit 2-073. Since the greater part of the measurements from which
this number was calculated were also used in reducing the other
observations of the series, the error probably affects the other obser-
vations, and in a somewhat increased degree. This will account only
for a part of the difference between the observations and the formula.
The remaining part of the differences in this series, and the somewhat
smaller differences in the next, may be due to the fact that the
experiments of both series were conducted with descending temper-
atures. Yet the experiments of the third column, which were made
by Dumas' method, do not exhibit any preponderance of positive
values for the excess of observed density, but rather the opposite.
TABLE VI.— ACETIC ACID.
EXPERIMENTS OF PLAYFAIR AND WANKLYN.
Tempera-
ture.
Pressure.
Density
calculated
by eq. (12).
Density observed.
I. II. HL
Excess of observed density.
I. II. HL
212-5
322-8
2-124
2-060
-•064
194
326-0
2-168
2-055
-•113
186
254-4
2-173
1-936
-•237
182
319-4
2-213
2-108
-•105
166-5
289-5
2-293
2-350
+ •057
163
245-8
2-290
2-017
-•273
132
227-5
2-628
2-292
-•336
130-5
285-7
2-729
2-426
- '303
119
269-0
2-914
2-623
-•291
116-5
211-3
2-876
2-371
-•505
95-5
(123-8)
3-105
2-594
-•511
86-5
(200-4)
3-432
3-172
-•260
79-9
(83-3)
3-297
3-340
+ •043
62-5
(46-2)
3-473
3-950
+ •477
On the whole, these experiments furnish no decisive indication of
any influence of the hydrogen or air upon the vapor. They may be
thought to corroborate slightly the tendency observed in the experi-
ments of Naumann and Troost toward lower densities than the
formula gives at very low pressures. Yet where the experiments
of Naumann show the greatest deficiency in observed density (at
78° and 80mm), an experiment of Playfair and Wanklyn, at almost
precisely the same temperature and pressure, gives a trifling excess
of observed density, and at a little lower temperature and pressure,
where we should expect from the experiments of Naumann that the
deficiency would be still greater, an experiment of Playfair and
Wanklyn shows a great excess of density.
By combining the experiments of Cahours, Naumann and Troost,
we may obtain observations of density at 130° for a very wide range
of pressures. For one atmosphere, we may regard the formula as
coinciding with the average of the numbers given by Cahours. For
pressures between three-quarters and one-half of an atmosphere the
experiments of Naumann show an excess of density; at pressures
394 VAPOR-DENSITIES.
below half an atmosphere the experiments both of Naumann and of
Troost show a deficiency of density as compared with the formula.
For an indefinite diminution of pressure, there can be little doubt that
the real density, like the value given by the formula, approaches the
theoretical value 2'073. The greatest excess in numbers obtained by
experiment is '07 ; the greatest deficiency is "19, which occurs at
59'7mm ; the next in order of magnitude is *11, which occurs more than
once. These discrepancies are certainly such as may be accounted
for by errors of observation. They do not appear to be greater than
we might expect on the hypothesis of the entire correctness of the
formula. On the other hand, the agreement is greater than we should
expect, if we reject the theory on which the formula was obtained.
It is about such as we might expect in a suitable formula of inter-
polation with three constants, which have been determined by the
values of the density for one atmosphere, for half an atmosphere, and
for infinitesimal pressures. But we must regard the actual formula,
in its application to this single temperature, as having only two
constants, of which one is determined so as to make the formula give
the theoretical value for infinitesimal pressures, and the other so as to
make it agree with the experiments of Cahours at the pressure of one
atmosphere.
An entirely different method has been employed by Horstmaim*
to determine the vapor-density of this substance. A current of dried
air is forced through the liquid acid, which is heated to promote
evaporation, and the mixture of air and vapor is cooled to any olesired
temperature, with deposition of the excess of acid, by passing upward
through a spiral tube in a suitable bath. The acid is then separated
from the air, and the quantity of each determined. It is assumed that
the air is exactly saturated with vapor on leaving the coil, and that it
has the temperature of the bath. If we know the pressure of saturated
vapor for that temperature, and assume the validity of Dalton's law,
it is easy to calculate the density of the vapor. For the pressure
of the air is found by subtracting the pressure of the vapor from
the total pressure (the experiments were so conducted that this
was the same as the actual pressure of the atmosphere), and the
ratio of the weights of the acid and the air obtained by analysis,
divided by the ratio of their pressures, will give the ratio of their
densities. The pressures of saturated vapor employed by Horstmann
are those given by Landolt,t and differ greatly from the determina-
tions of Regnault, in some cases being nearly twice as great, — a
difference noticed but not explained by Landolt, who however gives
* Berichte der deutschen chemischen GeadlscTiaft, Jahrg. iii (1870), S. 78 ; and Jahrg. xi
(1878), 'S. 1287.
t Lieb. Ann., suppl. vi (1868), p. 157.
VAPOR-DENSITIES. 395
determinations (previously unpublished) of Wiillner, which somewhat
exceed his own. (On the other hand, the observations of Bineau
substantially agree with those of Regnault.)
If we compare the observations of Horstmann with the values given
by equation (12), on the basis of Landolt's pressures, we find a very
marked disagreement, as may be seen by the following numbers,
which relate to the highest temperatures of Horstmann's experiments,
where the disagreement is least : —
Temperature - - 63'1 62-9 59'9 51 '1 49'0 487 44 -6 41'4
Pressure (Land.) - HO'O 109*2 97*0 69*0 63'4 63*0 53'1 46'6
Density cale. eq. (12) - 3'67 3*67 3'69 375 377 377 379 3-81
Density obs. - 3'19 3'11 3'12 3'16 2-89 2'98 275 2-62
It will be observed that while the values obtained from equation (12)
increase with diminishing temperatures, the values obtained from
Horstmann's experiments diminish. This diminution continues as
far as the experiments go, until finally at 12° or 15° the densities
are only one half as great as those obtained by Bineau, by direct
experiment at the same temperatures and at somewhat less pressures,
in a series of observations which bear every mark of a very excep-
tional precision. (Compare Tables VII and IV.) The explanation
of this disagreement is doubtless to be found in the values of the
pressures employed in the calculations, and it will be interesting to
see how the results may be modified by the adoption of different
pressures.
In determinations of the pressure of saturated vapors, too great
values are so much more easily accounted for than errors in the
opposite direction, especially when the pressures are small, that
especial interest attaches to the lowest figures which are supported by
a competent authority. The experiments of Regnault* were made
with three different preparations of acetic acid, of which the second
was once, and the third twice, purified by distillation over anhydrous
phosphoric acid. Each distillation considerably diminished the pressure
of the saturated vapor, the effect of the second distillation being about
half that of the first. The numbers obtained with the third prepara-
tion are given in the following table with their logarithms, and the
differences of the logarithms for one degree of temperature : —
Temperature. Pressure. log. pressure. diff. per 1*.
971 6-42 -8075
12-12 7-33 '8651
14-33 8-42 -9253
14-87 8-59 '9340
17-23 9-85 -9934
19-84 11-455 1-0590
22-37 13-15 1-1189
25-28 15-36 1'1864
* M6m. Acad. Sciences, vol. xxvi, p. 758. The experiments date from 1844.
396
VAPOR-DENSITIES.
The uniformity of the numbers in the last column shows the remark-
able precision of the determinations. At the same time it is evident
that the differences in these numbers are due principally to the errors
of observation, so that numbers obtained by interpolation between the
logarithms of the observed pressures will be somewhat better (on
account of averaging of the errors) than the original determinations.
The values obtained by such an interpolation have been used for
the comparison of Horstmann's experiments with the formula (12)
which is given in Table VII. Unfortunately this comparison cannot
be extended above 25°, which is the limit of Regnault's experiments.
The first three columns of the table give the temperatures of Horst-
mann's experiments, the pressures corresponding to these temperatures
according to the determinations of Landolt, and the density deduced
from Horstmann's experiments by the use of these pressures. To
TABLE VII. — ACETIC ACID.
Determinations of Vapor-density by Distillation.
Temper-
ature.
Pressure
ace. to
Landult.
Density
observed,
Horstmann
and Landolt.
Pressure
ace. to
Regnault.
Density
calc. from
Regnault's
pressures
by eq. (12).
Density
observed,
Horstmann
and Regnault
Excess of
observed density.
I. II.
25-0
23-5
2-42
15-13
3-86
3-80
-•06
23-8
22-4
2-23
14-19
3-86
3-56
-•30
22-6
21-6
2-29
13-31
3-87
3-76
-•11
21-5
20-4
2-24
12-54
3-87
3-68
-•19
20-4
19-2
2-05
11-81
3-88
3-37
-•51
20-2
19-0
2-28
11-68
3-88
3-75
-•13
20-0
18-9
2-13
11-56
3-88
3-52
-•36
17-4
16-8
2-09
9-95
3-89
3-56
-•33 «
15-6
15-6
1-98
S-96
3-90
3^48
-•42
15-3
15'3
1-95
8-81
3-90
3-42
-•48
15-3
15-3
1-85
8-81
3-90
3-24
-•66
14-7
15-1
1-78
8-54
3-91
3-18
-•73
12-7
13-7
1-96
7-60
3-91
3-56
-•35
12-4
13-5
1-89
7-46
3-92
3-45
-•47
these columns, which are taken from Horstmann's paper, are added
the pressure derived from Regnault's observations by the logarithmic
interpolation described above, the density calculated by equation (12)
from these pressures and the temperatures of the first column, and
the densities obtained by combining Horstmann's experiments with
Regnault's pressures. This column is derived from the second, third
and fourth, as follows. If w and W denote respectively the weights
of vapor and of air which pass through the apparatus in the same
time, P the height of the barometer, and p^ the pressure of saturated
vapor as determined by Landolt, the densities obtained on the basis of
Landolt's pressures, and given in the third column, are evidently repre-
w(P — p L)
sented by w *^' . The numbers of the fifth column, which are
. PL wiP — D }
represented in the same way by vw *R', where pR denotes the
VAPOR-DENSITIES. 397
pressure as determined by Regnault's experiments, have been cal-
culated by the present writer by multiplying the numbers of the
third column by
As the height of the barometer in Horstmann's experimente is not
given, it has been necessary to assume P = 760. The inaccuracy due
to this circumstance is evidently trifling. The last two columns of
the table, which relate to different series of experiments by Horstmann
(a distinction not observed in other parts of the table), give the excess
of the densities thus obtained from Horstmann's and Regnault's
experiments above the values calculated from equation (12) with the
use of Regnault's determinations of pressure.
The densities obtained by experiment are without exception less
than those obtained from equation (12). At the highest temperatures,
where the liability to error is the least, both in respect to the measure-
ment of the pressure of saturated vapor and in respect to the analysis
of the product of distillation, the results of experiment are most
uniform, and most nearly approach the numbers required by the
formula. At the lowest temperatures, the greatest observed density
is about one-eleventh less than that required by the formula, the
difference being about the same as between the highest and lowest
observed values for the same temperature.
Since each successive purification of the substance employed by
Regnault diminished the pressure of its vapor, it is not improbable
that the pressures might have been still farther diminished by farther
purification of the substance. The pressures which we have used are
therefore liable to the suspicion of being too high, and it is quite
possible that more accurate values of the pressure would still farther
reduce the deficiency of observed density.
Perchloride of phosphorus. — For this substance, we have at
atmospheric pressure a single determination of vapor-density by
Mitscherlich,* and a series of determinations by Cahours;t at lower
pressures we have determinations by WurtzJ and by Troost and
Hautefeuille.§ In the experiments of Wurtz the pressure was reduced
by mixing the vapor with air. In Table VIII all these determinations
are compared with the formula
- 3*6) 5441
The differences between the calculated and observed values are often
large, in six cases exceeding '30; but they exhibit in general that
* Pogg. Ann., vol. xxix (1833), p. 221.
t Com/ptes Rendus, vol. xxi (1845), p. 625 ; and Annales de Chimie et de Physique,
ser. 3, vol. xx (1847), p. 369.
£ Gomptes Eendus, vol. Ixxvi (1873), p. 601. § Ibid., vol. Ixxxiii (1876), p. 977.
398
VAPOR-DENSITIES.
irregularity which is characteristic of errors of observation. We
should expect large errors in the observed densities, on account of the
difficulty of obtaining the substance in a state of purity, and because
the large value of the density renders it very sensitive to the effect of
impurities which diminish the density, — also because the specific heat
of the vapor is great, as shown by the numerator of the fraction in
the second member of (13),* and because the density varies very
rapidly with the temperature as seen by the numbers in the third
column of Table VIII.
TABLE VIII. — PERCHLORIDE OF PHOSPHORUS.
EXPERIMENTS OF MITSCHEBLICH, CAHOURS, WURTZ, AND TROOST
AND HAUTEFEUILLE.
Tempera-
Pressure.
Density
calculated
Density
observed.
Excess of observed density.
ture.
by eq. (13).
Mitscherlich.
Cahours.
Mitscherlich.
Cahours.
336
(760)
3-610
3-656
+ •046
327
754
3-614
3-656
+ •042
300
765
3-637
3-654
+ •017
289
(760)
3-656
3-69
+ •034
288
763
3-659
3-67
+ •011
274
755
3-701
3-84
+ •139
250
751
3-862
3-991
+ •129
230
746
4-159
4-302
+ •142
222
753
4-344
4-85
+ •506
208
(760)
4-752
4-73
-•021
200
758
5-018
4-851
-•167
190
758
5-368
4-987
-•381
182
757
5-646
5-078
-•568
Wurtz.
T. &H.
Wurtz.
T.&H.
178*5
227-2
5-053
5-150
+ •097
175-8
253-7
5-223
5-235
+ •012
167-6
221-8
5-456
5-415
-•041
154-7
221
5-926
5-619
-•307
150-1
225
6-086
5-886
-•200
148-6
244
6-169
5-964
-•205
145
391
6-45
6-55
+ •10
145
311
6-37
6-70
+ •33
145
307
6-36
6-33
-•03
144-7
247
6-287
6-14
-•147
137
281
6-53
6-48
-•05
137
269
6-51
6-54
+ •03
137
243
6-48
6-46
-•02
137
234
6-47
6-42
-•05
137
148
6-31
6-47
+ •16
129
191
6-59
6-18
-•41
129
170
6-56
6-63
+ •07
129
165
6-55
6-31
-•24
But at the two lowest temperatures of Cahours' experiments, the
differences of the observed and calculated densities ('381 and -568) are
not only great, but exhibit, in connection with the adjacent numbers,
a regularity which suggests a very different law from that of the
* Compare Equilib. Het. Subs., this volume p. 180, and supra pp. 380-382.
VAPOR-DENSITIES. 399
formula. In fact, the densities obtained by Cahours at atmospheric
pressure and those obtained by Troost and Hautefeuille at pressures
a little less than one-third of an atmosphere seem to form a continuous
series, notwithstanding the abrupt change of pressure. Yet it is
difficult to admit that the density is independent of the pressure. So
radical a difference between the behavior of this substance and that of
the others which we have been considering requires unequivocal evi-
dence. Now it is worthy of notice that the experiment at 182°, in
which the greatest discrepancy is seen, is not given in the first record
of the experiments, which was in the Cwnptes Rendus in 1845. It is
given in the Annales de Chimie et de Physique in 1847, where it is
called the first experiment. (The experiment at 336° is also omitted
in the Comptes Rendus and that at 208° in the Annales, — otherwise
the lists are the same.) If it was the first experiment in point of time,
which is apparently the meaning, it was made before the publication
in the Comptes Rendus, and we can only account for its omission" by
supposing that it was a preliminary experiment, in which its distin-
guished author did not feel sufficient confidence to include it at first
with his other determinations, although he afterwards concluded to
insert it. If we reject this observation as doubtful, the disagreement
between the formula and observation appears to be within the limits
of possible error, but additional experiments will be necessary to
confirm the formula.*
Experiments have also been made by M. Wurtz in which the vapor
of the perchloride of phosphorus was diluted with that of the proto-
chloride.t These experiments may be used to test equation (8),
which, when the values of its constants are determined by equation
(13), reduces to the form
log A = JJ« -18-751, (14)
6
where p5, p2, and p3 denote the partial pressures due respectively to
the PC15, the C12, and the PC13, existing as such in the gas-mixture.
Since these quantities cannot be the subjects of immediate observa-
tion, a farther transformation of the equation will be convenient.
Let M8, M2 denote the quantities of the protochloride and of chlorine
of which the mixture may be formed, and P3, P2 the pressure which
* Additional experiments on the density of this vapor have been made by M. Cahours,
concerning which he says in 1866 : " Les determinations qui je viens d'effectuer a 170 et
172 degres (ce corps bout vers 160 a 165 degre"s) m'ont donn4 des nombres qui, bien que
notablement plus forts que ceux que j'ai obtenus ante'rieurement & 182 et 185 degr&,
sont encore bien eloignes de celui que correspond £ 4 volumes," Comptes Rendus, t. 63,
p. 16. So far as the present writer has been able to ascertain, these determinations
have not been published. The formula gives 6 '025 for 170° and 5*973 for 172°, at
atmospheric pressure. The number corresponding to four volumes is 7*20.
t Comptes Rendiu, vol. Ixxvi (1873), p. 601.
400
VAPOR-DENSITIES.
would belong to each of these if existing by itself with the same
volume and temperature. These quantities will be connected by the
equations
,1 -.
* 2-22v' 3~
where k denotes the same constant as on page 381. From the evident
relations
we obtain
and by substitution of these values in equation (14),
5441
log
13-751.
(16)
In view of the relations (15), this may be regarded as an equation
between the pressure, the temperature, the volume, and the quantities
of protochloride of phosphorus and chlorine into which the gas-
mixture is resolvable.
TABLE IX. — PERCHLORIDE AND PROTOCHLORIDE OF PHOSPHORUS.
EXPERIMENTS ON THE MIXED VAPORS BY WURTZ.
No. of
ezp.
tc
p
(obs.)
7T
S
P2
PS
p
calculated
by eq. (16).
Excess
of obs. value
of p.
XII
173-29
756-1
423
6-68
392-4
725-5
760-7
-4-6
X
165-4
748-4
413
6-80
390-1
725-5
747-9
+ -5
VII
176-24
751-0
411
6-88
392-7
732-7
773-1
-22-1
VIII
169-35
724-1
394
7-16
391-8
721-9
750-5
' -26-4
V
175-26
743-3
343
7-03
334-9
735-2
764-4
-21-1
n
164-9
758-5
338
7-38
346-4
766-9
782-9
-24-4
XI
175-75
760-0
318
7-00
309-2
751-2
776-8
-16-8
IV
175-26
756-3
271
7-06
265-7
751-0
770-9
-14-6
IX
160-47
753-5
214
7-44
221-1
760-6
766-8
-13-3
i
165-4
760-0
194
7-25
195-3
761-3
768-5
- 8-5
VI
170-34
751-2
174
8-30
200-6
777-8
787-6
-36-4
in
174-28
742-7
168
7-74
180-6
755-3
766-5
-23-8
It is in this form that we shall apply the equation to the experiments
of M. Wurtz, the results of which are exhibited in Table IX. The
first column gives the number distinguishing each experiment in the
original memoir ; the second, the temperature ; the third, the observed
pressure (p) of the mixture of PC15, PC13, and C12, which is the
barometric pressure corrected for the small quantity of air remaining
in the flask ; the fourth, the pressure TT due to the possible perchloride,
found by subtracting the pressure due to the excess of protochloride
(this pressure is calculated from the theoretical density of the proto-
chloride) from the total pressure ; the fifth, the density 8 of the
possible perchloride calculated from its pressure TT with the tem-
perature and volume. The numbers of these five columns are taken
VAPOR-DENSITIES. 401
from the memoir cited, except that the correction of the barometric
pressures has been applied by the present writer in accordance with
the data furnished in that memoir. The two next columns contain
the values of P2 and P3. These would naturally be calculated from
M2 and M3 by equations (15). But since the values of M2 and M8
have not been given explicitly, those of P2 and P8 have been calculated
from the recorded values of ?r and 8. Since the weight of the possible
7*2
perchloride is ^^M2, we have
7'2M2ta_7-2
= 2-22v7r== TT 3>
Moreover,
P-7T = P3-P2,
since both members of the equation express the pressure due to the
excess of the protochloride. The values of P2 and P3 were obtained
by these equations.
The eighth column of the table gives the values of p calculated
from the preceding values of tc, P2, and P3, by equation (16); and the
last column, the difference of the observed and calculated values of p.
The average difference is 18mm, or a little more than two per cent., the
observed pressure being almost uniformly less than the calculated
value. This deficiency of pressure is doubtless to be accounted for
by a fact which MM. Troost and Hautefeuille have noticed in this
connection. The protochloride of phosphorus deviates quite appre-
ciably from the laws of Mariotte, Gay-Lussac, and Avogadro, the
product of the volume and pressure of a given quantity of vapor at
180° and the pressure of one atmosphere being 1*548 per cent, less
than at the same temperature and the pressure of one-half an atmo-
sphere.* Now we may assume as a general rule that when the
product of volume and pressure of a gas is slightly less than the
theoretical number (calculated by the laws of Mariotte, Gay-Lussac,
and Avogadro) the difference for any same temperature is nearly pro-
portional to the pressure.! It is therefore probable that between
160° and 180°, at pressures of about one atmosphere, the product of
volume and pressure for protochloride of phosphorus is somewhat
more than three per cent, less than the theoretical number. The
experiments of Wurtz, as exhibited in Table IX, show that the
pressure, and therefore the product of volume and pressure (we may
evidently give the volume any constant value as unity), in a mixture
consisting principally of the protochloride is on the average a little
more than two per cent, less than is demanded by theory, the differ-
ences being greater when the proportion of the protochloride is
* Troost and Hautefeuille, Comptes fiendus, vol. Ixxxiii (1876), p. 334.
t Andrews, " On the Gaseous State of Matter," Phil. Trans., vol. clxvi (1876), p. 447.
G.I. 20
402 VAPOR-DENSITIES.
greater. The deviation from the calculated values is therefore in
the same direction and about such in quantity as we should expect.*
M. Wurtz has remarked that the average value of S (the density
of the possible perchloride) is nearly identical with the theoretical
density of the perchloride, and appears inclined to attribute the
variations from this value to the errors of experiment. Yet it appears
very distinctly in Table IX, in which the experiments are arranged
according to the value of TT (the pressure due to the possible per-
chloride), that S increases as TT diminishes. The experiments of
MM. Troost and Hautefeuille show that the coincidence remarked by
M. Wurtz is due to the fact that on the average in these experiments
the deficiency of the density of the possible perchloride (compared
with the theoretical value) is counterbalanced by the excess of density
of the protochloride. When TT > 400, the effect of the deficiency in
the density of the possible perchloride distinctly preponderates ; when
TT < 250, the effect of the excess of density in the protochloride
distinctly preponderates. But the magnitude of the differences con-
cerned is not such as to invalidate the general conclusion established
by the experiments of M. Wurtz, that the dissociation of the per-
chloride may be prevented (at least approximately) by mixing it with
a large quantity of the protochloride.
Table for facilitating calculation. — The numerical solution of equa-
tions (10), (11), (12) and (13) for given values of t and p may be
facilitated by the use of a table. If we set
(17)
lOOOD^D-D,) , lOOO(A-l)
L - lo " = lQS (2 -Ay '
we have for peroxide of nitrogen,
L=|^J|+logp- 9-451; (19)
for formic acid,
L=^3+logp-9-641; (20)
for acetic acid,
OKOA
(21)
* The deviation of the protochloride of phosphorus from the laws of ideal gases shows
the impossibility of any very close agreement between such equations as have been
deduced in this paper and the results of experiment in the case of gas-mixtures in which
this substance is one of the components. With respect to the question whether future
experiments on the vapor of the perchloride (alone, or with an excess of chlorine or of
the protochloride) will reduce the disagreement between the calculated and observed
values to such magnitudes as occur in the case of the protochloride alone, it would be
rash to attempt to anticipate the result of experiment.
VAPOR-DENSITIES.
and for perchloride of phosphorus,
403
<22>
By these equations the values of L are easily calculated. " The values
of A may then be obtained by inspection (with interpolation when
necessary) of the following table. From A the value of D may be
obtained by multiplying by Dx, viz., by T589 for peroxide of nitrogen
or formic acid, by 2*073 for acetic acid, and by 3'6 for perchloride of
phosphorus.*
TABLE X.
For the solution of the equation: W100Q(A~1)_T
(2-A)a
L
A
Diff.
L
A
Diff.
L
A
Diff.
•7
1-005
1
3-0
1-382
g\f\
5-3
1932
•8
1-006
L
3-1
1-421
39
A f\
5-4
1-939
7
•9
1-008
3-2
1-461
40
• i / »
5-5
1-945
6
1-0
1-010
3-3
1-500
39
OT
5-6
1-951
6
1-1
1-012
3-4
1-537
37
• > —
5-7
1-956
5
1-2
1-015
4'
3-5
1-574
37
Off
5-8
1-961
5
1-3
1-019
3-6
1-609
35
OO
5-9
1-965
4
1-4
1-024
3-7
1-642
SB
O1
6-0
1-969
4
1-5
1-6
1-030
1-037
7
3-8
3-9
1-673
1-703
31
30
OT
6-1
6-2
1-972
1-975
3
3
1-7
1-8
1-9
2-0
2-1
2-2
2-3
2-4
1-046
1-056
1-069
1-084
1-102
1-122
1-146
1-172
10
13
15
18
20
24
26
Qft
4-0
4-1
4-2
4-3
4-4
4-5
4-6
4-7
1-730
1-755
1-778
1-800
1-819
1-837
1-854
1-868
27
25
23
22
19
18
17
14
1 4
6-3
6-4
6-5
6-6
6-7
6-8
6-9
7-0
1-978
1-980
1-982
1-984
1-986
1-987
1-989
1-990
2
2
2
2
1
2
1
2-5
2-6
1-202
1-234
O\J
32
Q4.
4-8
4-9
1-882
1-894
14
12
7-2
7-4
1-992
1-994
2-7
1-268
o't
07
5-0
1-905
i n
7-6
1-995
2-8
1-305
Oi
QO
5-1
1-915
10
7-8
1-996
2-9
1-343
00
on
5-2
1-924
8-0
1-997
3-0
1-382
«jy
5-3
1-932
9-0
1-999
The constants of these equations are of course subject to correction
by future experiments, which must also decide the more general
question — in what cases, and within what limits, and with what
degree of approximation, the actual relations can be expressed by
equations of such form. In the case of perchloride of phosphorus
especially, the formula proposed requires confirmation.
* The value of A diminished by unity expresses the ratio of the number of the mole-
cules of the more complex type to the whole number of molecules. Thus, if A=l-20,
in the case of peroxide of nitrogen there are 20 molecules of the type N2O4 to 80 of the
type N02, or in the case of perchloride of phosphorus there are 20 molecules of the type
PC15 to 40 of the type PC13 and 40 of the type CLj. A consideration of the varying
values of A is therefore more instructive than that of the values of D, and it would in
some respects be better to make the comparison of theory and experiment with respect
to the values of A.
VI.
ON AN ALLEGED EXCEPTION TO THE SECOND LAW OF
THERMODYNAMICS.
[Science, vol. i, p. 160, Mar. 16, 1883.]
ACCORDING to the received doctrine of radiation, heat is transmitted
with the same intensity in all directions and at all points within any
space which is void of ponderable matter and entirely surrounded
by stationary bodies of the same temperature. We may apply this
principle to the arrangement recently proposed by Prof. H. T. Eddy *
for transferring heat from a colder body A to a warmer B without
expenditure of work.
In its simplest form the arrangement consists of parallel screens,
which are placed between the bodies A and B, and have the form of
very thin disks with certain apertures, and the property of totally
reflecting heat. These disks, or screens, are supposed to be fixed on
a common axis, and to revolve with a constant velocity. For the
purposes of theoretical discussion, we may allow this velocity to be
kept up without expenditure of work, since we may suppose the
experiment to be made in vacuo. If the dimensions and velocity of
the apparatus are such that the screens receive a considerable change
of position during the time in which radiant heat traverses the
distances between them, the apertures in the screens may be so placed
that radiations can pass from A to B, but not from B to A. It
is inferred that it is possible, by such means, to make heat pass from
a colder to a warmer body without compensation.
In order to judge of the validity of this inference, let us suppose
thermal equilibrium to subsist initially in the system, and inquire
whether the motion of the screens will have any tendency to disturb
that equilibrium. We suppose, then, that the screens, the bodies A
and B, and the walls enclosing the space in which the experiment is
made, have all the same temperature, and that the spaces between
and around the screens and the bodies A and B are filled with the
radiations which belong to that temperature, according to the prin-
ciple cited above. Under such circumstances, it is evident that the
presence of the screens, whether at rest or in motion, will not have
* Journ. Frankl. Inst., March, 1883.
EXCEPTION TO SECOND LAW OF THERMODYNAMICS. 405
any influence upon the intensity of the radiations passing through
the spaces between and around them; since the heat reflected by a
screen in any direction is the exact equivalent of that which would
proceed in the same direction (without reflection) if the screen were
not there. So, also, the heat passing through any aperture in a screen
is the exact equivalent of that which would be reflected in the same
direction if there were no aperture. The quantities of radiant heat
which fall upon the bodies A and B are therefore entirely unchanged
by the presence and the motion of the screens, and their temperature
cannot be affected.
We may conclude a fortiori that B will not grow warmer if A
is colder than B, and none of the other bodies present are warmer
than B.
Since the body A, for example, when the screens are in motion,
does not receive radiations from every body to which it sends them,
it is not without interest to inquire from what bodies it will receive
its share of heat. This problem may be solved most readily by sup-
posing the screens to move in the opposite direction, with the same
velocity as before. One may easily convince himself that every body
which receives radiant heat from A when the apparatus moves back-
ward, will impart heat to A when the apparatus moves forward, and
to exactly the same amount, if its temperature is the same as that
of A.
VII.
ELECTROCHEMICAL THERMODYNAMICS.
Two letters to the Secretary of the Electrolysis Committee of the
British Association for the Advancement of Science.
[Report Brit. Asso. Adv. Sci, 1886, pp. 388, 389 ; and 1888, pp. 343-346.]
New Haven, Janua/ry 8, 1887.
Professor OLIVER J. LODGE,
Dear Sir, — Please accept my thanks for the proof copy of your
" Report on Electrolysis in its Physical and Chemical Bearings," which
I received a few days ago with the invitation, as I understand it, to
comment thereon.
I do not know that I have anything to say on the subjects more
specifically discussed in this report, but I hope I shall not do violence
to the spirit of your kind invitation or too much presume on your
patience if I shall say a few words on that part of the general subject
which you discussed with great clearness in your last report on
pages 745 ff. (Aberdeen). To be more readily understood, I shall
use your notation and terminology, and consider the most simple case
possible.
Suppose that two radicles unite in a galvanic cell during the
passage of a unit of electricity, and suppose that the same quantities
of the radicles would give Oe units of heat in uniting directly, that is,
without production of current ; will the union of the radicles in the
galvanic cell give J0e units of electrical work ? Certainly not, unless
the radicles can produce the heat at an infinitely high temperature,
which is not, so far as we know, the usual case. Suppose the highest
temperature at which the heat can be produced is t", so that at this
temperature the union of the radicles with evolution of heat is a
reversible process; and let t' be the temperature of the cell, both
temperatures being measured on the absolute scale. Now Oe units
j.'
of heat at the temperature t" are equivalent to #6777 units of heat at
I/
A/r j.t
the temperature t't together with J0e— -77- units of mechanical or
t
electrical work. (I use the term "equivalent" strictly to denote
ELECTROCHEMICAL THERMODYNAMICS. 407
reciprocal convertibility, and not in the loose and often misleading
sense in which we speak of heat and work as equivalent when there
is only a one-sided convertibility.) Therefore the rendement of a
t" — t'
perfect or reversible galvanic cell would be J0e - '- units of electrical
t' t
work, with #677-, units of (reversible) heat, for each unit of electricity
which passes.
You will observe that we have thus solved a very different problem
from that which finds its answer in the Joule- Helmholtz- Thomson
equation with term for reversible heat. That equation gives a
relation between the E.M.F. and the reversible heat and certain other
quantities, so that if we set up the cell and measure the reversible
heat, we may determine the E.M.F. without direct measurement, or
vice versa. But the considerations just adduced enable us to predict
both the electromotive force and the reversible heat without setting
up the cell at all. Only in the case that the reversible heat is zero
does this distinction vanish, and not then unless we have some way
of knowing d priori that this is the case.
From this point of view it will appear, I think, that the pro-
duction of reversible heat is by no means anything accidental, or
superposed, or separable, but that it belongs to the very essence of
the operation.
The thermochemical data on which such a prediction of E.M.F. and
reversible heat is based must be something more than the heat of
union of the radicles. They must give information on the more
delicate question of the temperature at which that heat can be
obtained. In the terminology of Clausius they must relate to entropy
as well as to energy — a field of inquiry which has been far too much
neglected.
Essentially the same view of the subject I have given in a form
more general and more analytical, and, I fear, less easily intelligible,
in the closing pages of a somewhat lengthy paper on the " Equilibrium
of Heterogeneous Substances " (Conn. Acad. Trans., vol. iii, 1878), of
which I send you the Second Part, which contains the passage in
question. My separate edition of the First Part has long been
exhausted. The question whether the " reversible heat " is a negligible
quantity is discussed somewhat at length on pages 510-519.* On
page 503t is shown the connection between the electromotive force
of a cell and the difference in the value of (what I call) the potential
for one of the ions at the electrodes. The definition of the potential
for a material substance, in the sense in which I use the term, will be
found on page 443 j of the synopsis from the Am. Jowr. Sci., vol. xvi,
which I enclose. I cannot say that the term has been adopted by
* [This vol. , pp. 339-347. ] t [Ibid. , p. 333. J J [Ibid. , p. 356. ]
408
ELECTROCHEMICAL THERMODYNAMICS.
physicists. It has, however, received the unqualified commendation
of Professor Maxwell (although not with reference to this particular
application — see his lecture on the "Equilibrium of Heterogeneous
Substances," in the science conferences at South Kensington, 1876);
and I do not see how we can do very well without the idea in certain
kinds of investigations.
Hoping that the importance of the subject will excuse the length of
this letter,
I remain,
Yours faithfully,
J. WILLARD GIBBS.
New Haven, November 21, 1887.
Professor OLIVER J. LODGE,
Dear Sir, — As the letter which I wrote you some time since con-
cerning the rendement of a perfect or reversible galvanic cell seems to
have occasioned some discussion, I should like to express my views a
little more fully.
It is easy to put the matter in the canonical form of a Carnot's
cycle. Let a unit of electricity pass through the cell producing
certain changes. We may suppose the cell brought back to its
original condition by some reversible chemical process, involving a
certain expenditure (positive or negative) of work and heat, but
involving no electrical current nor any permanent changes in other
bodies except the supply of this work and heat.
Now the first law of thermodynamics requires that the algebraic
sum of all the work and, heat (measured in " equivalent " units)
supplied by external bodies during the passage of the electricity
through the cell, and the subsequent processes by which the cell is
restored to its original condition, shall be zero.
And the second law requires that the algebraic sum of all the heat
received from external bodies, divided, each portion thereof, by the
absolute temperature at which it is received, shall be zero.
Let us write W for the work and Q for the heat supplied by ex-
ternal bodies during the passage of the electricity, and [W], [Q] for
the work and heat supplied in the subsequent processes.
Then
and
a)
(2)
where t under the integral sign denotes the temperature at which the
element of heat d[Q] is supplied, and tf the temperature of the cell,
which we may suppose constant.
ELECTROCHEMICAL THERMODYNAMICS. 409
Now the work W includes that required to carry a unit of electricity
from the cathode having the potential V" to the anode having the
potential V'. (These potentials are to be measured in masses of the
same kind of metal attached to the electrodes.) When there is any
change of volume, a part of the work will be done by the atmosphere
or other body enclosing the cell. Let this part be denoted by WP.
In some cases it may be necessary to add a term relating to gravity,
but as such considerations are somewhat foreign to the essential
nature of the problem which we are considering, we may set such
cases aside. We have then
W = V'-V" + WP (3)
Combining these equations we obtain
V" - V = WP + [ W] + [Q] - if . (4)
J *
It will be observed that this equation gives the electromotive force
in terms of quantities which may be determined without setting up
the cell.
Now [W] + [Q] represents the increase of the intrinsic energy of
the substances in the cell during the processes to which the brackets
relate, and *-/*•* represents their increase of entropy during the
same processes. The same expressions, therefore, with the contrary
signs, will represent the increase of energy and entropy in the cell
during the passage of the current. We may therefore write
V- V'= - Ae+f Afl + Wp, (5)
where Ae and A^ denote respectively the increase of energy and
entropy in the cell during the passage of a unit of electricity. This
equation is identical in meaning, and nearly so in form, with equation
(694) of the paper cited in my former letter, except that the latter
contains the term relating to gravity. See Trans. Conn. Acad.,
iii (1878), p. 509.* The matter is thus reduced to a question of
energy and entropy. Thus, if we knew the energy and entropy of
oxygen and hydrogen at the temperature and pressure at which they
are disengaged in an electrolytic cell, and also the energy and entropy
of the acidulated water from which they are set free (the latter, in
strictness, as functions of the degree of concentration of the acid), we
could at once determine the electromotive force for a reversible cell.
This would be a limit below which the electromotive force required in
an actual cell used electrolytically could not fall, and above which the
electromotive force of any such cell used to produce a current (as in a
Grove's gas battery) could not reach.
* [This volume, p. 338.]
410 ELECTROCHEMICAL THERMODYNAMICS.
Returning to equation (4), we may observe that if t under the
integral sign has a constant value, say t", the equation will reduce to
V - V = f/f -[Q] + [ W] + WP . (6)
Such would be the case if we should suppose that at the tem-
perature t" the chemical processes to which the brackets relate take
place reversibly with evolution or absorption of heat, and that the
heat required to bring the substances from the temperature of the cell
to the temperature t", and that obtained in bringing them back again
to the temperature of the cell, may be neglected as counterbalancing
each other. This is the point of view of my former letter. I do not
know that it is necessary to discuss the question whether any such
case has a real existence. It appears to me that in supposing such a
case we do not exceed the liberty usually allowed in theoretical
discussions. But if this should appear doubtful, I would observe
that the equation (6) must hold in all cases if we give a slightly
different definition to t", viz., if t" be defined as a temperature deter-
mined so that
t
The temperature t", thus defined, will have an important physical
meaning. For by means of perfect thermo-dynamic engines we may
change a supply of heat [Q] at the constant temperature t" into a
supply distributed among the various temperatures represented by t
in the manner implied in the integral, or vice versa. We may,
therefore, while vastly complicating the experimental operations
involved, obtain a theoretical result which may be very simply stated
and discussed. For we now see that after the passage of the current
we may (theoretically) by reversible processes bring back the cell to
its original state simply by the expenditure of the heat [Q] supplied
at the temperature t", with perhaps a certain amount of work repre-
sented by [W], and that the electromotive force of the cell is
determined by these quantities in the manner indicated by equation
(6), which may sometimes be further simplified by the vanishing
of [W] and WP.
If the current causes a separation of radicles, which are afterwards
united with evolution of heat, [Q] being in this case negative, t"
represents the highest temperature at which this heat can be obtained.
I do not mean the highest at which any part of the heat can be
obtained — that would be quite indefinite — but the highest at which
the whole can be obtained. I should add that if the effect of the
union of the radicles is obtained partly in work — [W], and partly
in heat— [Q], we may vary the proportion of work and heat; and t"
ELECTROCHEMICAL THERMODYNAMICS. 411
will then vary directly as [Q]. But if the effect is obtained entirely
in heat, t" will have a perfectly definite value.
It is easy to show that these results are in complete accordance
with Helmholtz's differential equation. We have only to differentiate
the value which we have found for the electromotive force. For this
purpose equation (5) is most suitable. It will be convenient to write E
for the electromotive force V — V", and for the differences Ae, ki\ to
write the fuller forms e" — e', J/" — */, where the single and double
accents distinguish the values before and after the passage of the
current. We may also set p(v' — v") for WP, where p is the pressure
(supposed uniform) to which the cell is subjected, and v" — v' is the
increase of volume due to the passage of the current. If we also
omit the accent on the t, which is no longer required, the equation
will read
E = e" - e' - t(rfr - if) +p(v" - v'). (8)
If we suppose the temperature to vary, the pressure remaining con-
stant, we have
= de" -dff-t djj" + tdrf- (rff - vf) dt +p dv" -p dv'. (9)
Now, the increase of energy de is equal to the heat required to
increase the temperature of the cell by dt diminished by the work
done by the cell in expanding. Since drf is the heat imparted divided
by the temperature, the heat imparted is tdrf, and the work is
obviously p dv'. Hence
de' = tdrf— pdv',
and in like manner
If we substitute these values, the equation becomes
dE = (rj'-ri")dt (10)
We have already seen that r\ — r\' represents the integral -^J of
equations (2) and (4), which by equation (2) is equal to the reversible
heat evolved, — Q, divided by the temperature of the cell, which we
now call t. Substitution of this value gives
^=-§ (ID
dt t'
which is Helmholtz's equation.
These results of the second law of thermodynamics are of course
not to be applied to any real cells, except so far as they approach the
condition of reversible action. They give, however, in many cases
limits on one side of which the actual values must lie. Thus, if we
set ^ for = in equations (2), (4), (5), (6), and ^ for = in (8), the
formula will there hold true without the limitation of reversibility.
412 ELECTROCHEMICAL THERMODYNAMICS.
But we cannot get anything by differentiating an inequality, and it
does not appear d priori which side of (10) is the greater when the
condition of reversibility is not satisfied. The term -^ in (11) is
u
certainly not greater than rff — rf, for which it was substituted. But
tliis does not determine which side of (11) is the greater in case of
irreversibility. It is the same with Helmholtz's method of proof,
which is quite different from that here given, but indicates nothing
except so far as the condition of reversibility is fulfilled. (See
Sitzungsberidite Berl. Acad., 1882, pp. 24, 25.)
I fear that it is a poor requital for the kind wish which you
expressed at Manchester, that I were present to explain and support
my position, for me to impose so long a letter upon you. Trusting,
however, in your forbearance, I remain, yours faithfully,
J. WILLARD GIBBS.
VIII.
SEMI-PERMEABLE FILMS AND OSMOTIC PRESSURE.
[Nature, vol. LV, pp. 461, 462, Mar. 18, 1897.]
LORD KELVIN'S very interesting problem concerning molecules
which differ only in their power of passing a diaphragm (see Nature
for January 21, p. 272), seems only to require for its solution the
relation between density and pressure for the fluid at the temperature
of the experiment, when this relation for small densities becomes that
of an ideal gas ; in other cases, a single numerical constant in addition
to the relation between density and pressure is sufficient.
This will, perhaps, appear most readily if we imagine each of the
vessels A and B connected with a vertical column of the fluid which
it contains, these columns extending upwards until the state of an
ideal gas is reached. The equilibrium which we suppose to subsist
will not be disturbed by communications between the columns at as
many levels as we choose, if these communications are always made
through the same kind of semi-permeable diaphragm as that which
separates the vessels A and B. It will be observed tliat the difference
of level at which any same pressure is found in the two columns is
a constant quantity, easily determined in the upper parts (where the
fluids are in the ideal gaseous state) as a function of the composition
of the fluid in the A-column, and giving at once the height above the
vessel A, where in the A-column we find a pressure equal to that in
the vessel B.
In fact, we have in either column
dp= —yydz,
where the letters denote respectively pressure, force of gravity, density,
and vertical elevation. If we set
wehave
Integrating, with a different constant for each column, we get
414 SEMI-PERMEABLE FILMS AND OSMOTIC PRESSURE.
In the upper regions,
r(p)-i-*;
y P
where t denotes temperature, and a the constant of the law of Boyle
and Charles. Hence,
Moreover, if 1 : n represents the constant ratio in which the S- and
D-inolecules are mixed in the A-column, we shall have in the upper
regions, where the S-molecules have the same density in the two
columns,
Therefore, at any height,
This equation gives the required relation between the pressures in A
and B and the composition of the fluid in A. It agrees with vari't
Hoff's law, for when n is small the equation may be written
or
Pl-pB
But we must not suppose, in any literal sense, that this difference
of pressure represents the part of the pressure in A which is everted
by the D-molecules, for that would make the total pressure calculable
by the law of Boyle and Charles.
To show that the case is substantially the same, at least for any one
temperature, when the fluid is not volatile, we may suppose that we
have many kinds of molecules, A, B, C, etc., which are identical in all
properties except in regard to passing diaphragms. Let us imagine
a row of vertical cylinders or tubes closed at both ends. Let the first
contain A-molecules sufficient to give the pressure pf at a certain
level. Then let it be connected with the second cylinder through a
diaphragm impermeable to B-molecules, freely permeable to all others.
Let the second cylinder contain such quantities of A- and B-molecules
as to be in equilibrium with the first cylinder, and to have a certain
pressure p" at the level of p' in the first cylinder. At a higher level
this second cylinder will have the pressure which we have called p'.
There let it be connected with the third cylinder through a diaphragm
impermeable to C-molecules, and to them alone. Let this third
cylinder contain such quantities of A-, B-, and C-molecules as to be
in equilibrium with the second cylinder, and have the pressure p" at
the diaphragm ; and so on, the connections being so made, and the
SEMI-PERMEABLE FILMS AND OSMOTIC PRESSURE. 415
quantities of the several kinds of molecules so regulated, that the
pressures at all the diaphragms shall have the same two values.
It is evident that the vertical distance between successive con-
nections must be everywhere the same, say I ; also, that at all the
diaphragms, on the side of the greater pressure, the proportion of
molecules which can and which cannot pass the diaphragm must be
the same. Let the ratio be l:n. If we write yA, yB, etc., for the
densities of the several kinds of molecules, and y for the total
density, we have for the second cylinder
For the third cylinder we have this equation, and also
yA+yB+yo = 1 +
VA+ys
which gives
In this way, we have for the rth cylinder
Now the vertical distance between equal pressures in the first and
rth cylinders, is
(r-l)l.
Now the equilibrium will not be destroyed if we connect all the
cylinders with the first through diaphragms impermeable to all except
A-molecules. And the last equation shows that as y/yA increases
geometrically, the vertical distance between any pressure in the
column when this ratio of densities is found, and the same pressure
in the first cylinder increases arithmetically. This distance, therefore,
may be represented by log(y/yA) multiplied by a constant. This is
identical with our result for a volatile liquid, except that for that
case we found the value of the constant to be at/g.
The following demonstration of van't Hoff's law, which is intended
to apply to existing substances, requires only that the solutum, i.e.,
dissolved substance, should be capable of the ideal gaseous state, and
that its molecules, as they occur in the gas, should not be broken up
in the solution, nor united to one another in more complex molecules.
It will be convenient to use certain quantities which may be called
the potentials of the solvent and of the solutum, the term being thus
defined : — In any sensibly homogeneous mass, the potential of any
independently variable component substance is the differential co-
efficient of the thermodynamic energy of the mass taken with respect
416 SEMI-PERMEABLE FILMS AND OSMOTIC PRESSURE.
to that component, the entropy and volume of the mass and the
quantities of its other components remaining constant. The advantage
of using such potentials in the theory of semi-permeable diaphragms
consists pirtly in the convenient form of the conditions of equilibrium,
the potential for any substance to which a diaphragm is freely per-
meable having the same value on both sides of the diaphragm, and
partly in our ability to express van't Hoff's law as a relation between
the quantities characterising the state of the solution, without reference
to any experimental arrangement (see Transactions of the Connecticut
Academy, vol. iii, pp. 116, 138, 148, 194) [this vol., pp. 63, 83, 92, 135].
Let there be three reservoirs, R', R", R'", of which the first contains
the solvent alone, maintained in a constant state of temperature and
pressure, the second the solution, and the third the solutum alone.
Let R' and R" be connected through a diaphragm freely permeable
to the solvent, but impermeable to the solutum, and let R" and R'"
be connected through a diaphragm impermeable to the solvent, but
freely permeable to the solutum. We have then, if we write fa and
yu2 for the potentials of the solvent and the solutum, and distinguish
by accents quantities relating to the several reservoirs,
f*i" = Pi = const., fa" = jjL2'".
Now if the quantity of the solutum in the apparatus be varied, the
ratio in which it is divided in equilibrium between the reservoirs R"
and R"7 will be constant, so long as its densities in the two reservoirs,
y.2", y2'", are small. For let us suppose that there is only a single
molecule of the solutum. It will wander through R" and R'", and in
a time sufficiently long the parts of the time spent respectively in
R" and R'", which for convenience we may suppose of equal volume,
will approach a constant ratio, say 1:B. isow if we put in the
apparatus a considerable number of molecules, they will divide them-
selves between R' and R" sensibly in the ratio 1 : B, so long as they
do not sensibly interfere with one another, i.e., so long as the number
of molecules of the solutum which are within the spheres of action of
other molecules of the solutum is a negligible part of the whole, both
in R" and R'". With this limitation we have, therefore,
72 =
Now in R'" let the solutum have the properties of an ideal gas, which
give for any constant temperature (ibid. p. 212) [this vol., p. 152]
where Oj is the constant of the law of Boyle and Charles, and C
another constant. Therefore,
SEMI-PEEMEABLE FILMS AND OSMOTIC PRESSURE. 417
This equation, in which a single constant may evidently take the
place of B and C, may be regarded as expressing the property of the
solution implied in van't HofFs law. For we have the general thermo-
dynamic relation (ibid. p. 143) [this vol., p. 88].
where v and r\ denote the volume and entropy of the mass considered,
and mj and m2 the quantities of its components. Applied to this
case, since t and fa are constant, this becomes
Substituting the value of d/u.2", derived from the last finite equation,
we have
whence, integrating from y2" = 0 and p" =p', we get
p"-p' = a2ty2",
which evidently expresses van't Hoff's law.
We may extend this proof to cases in which the solutum is not
volatile by supposing that we give to its molecules mutually repulsive
molecular forces, which, however, are entirely inoperative with respect
to any other kind of molecules. In this way we may make the
solutum capable of the ideal gaseous state. But the relations per-
taining to the contents of R" will not be affected by these new forces,
since we suppose that only a negligible part of the molecules of the
solutum are within the range of such forces. Therefore these relations
cannot depend on the new forces, and must exist without them.
To give up the condition that the molecules of the solutum shall
not be broken up in the solution, nor united to one another in more
complex molecules, would involve the consideration of a good many
cases, which it would be difficult to unite in a brief demonstration.
The result, however, seems to be that the increase of pressure is to be
estimated by Avogadro's law from the number of molecules in the
solution which contain any part of the solutum, without reference to
the quantity in each. J. WILLARD GIBBS.
New Haven, Connecticut, February 18.
G.I. 2D
IX.
UNPUBLISHED FRAGMENTS.
[Being portions of a supplement to the "Equilibrium of Heterogeneous
Substances " in preparation at the time of the author's death, and
intended to accompany a proposed reprint of his thermo-
dynamic papers*]
[A list of subjects found with the manuscript and printed below
appears to indicate the scope of the supplementary chapters as
planned by Professor Gibbs. As will be observed, however, the
authors unfinished manuscript, except for a number of dis-
connected notes, relates to only two of these subjects, the first and
fourth in the list]
On the values of potentials in liquids for small components. (Tem-
perature coefficients.)
On the fundamental equations of molecules with latent differences.
On the fundamental equations for vanishing components.
On the equations of electric motion.
On the liquid state, p = 0.
On entropy as mixed-up-ness.
Geometrical illustrations.
On similarity in thermodynamics.
Cryohydrates.
'[See Preface.]
UNPUBLISHED FRAGMENTS. 419
On the Values of Potentials in Liquids for Substances which
form but a Small Part of the whole Mass.*
The value of a potential! for a volatile substance in a liquid may
be measured in a coexistent gaseous phase, J and so far as the latter
may be treated as an ideal gas or gas-mixture, § the value of the
potential will be given by the equation (276), [" Equilib. Het. Subs."]
which may be briefly written
/z = func(0+ctflogyga8, [1]
where JUL is the potential of the volatile substance considered, either in
the liquid or in the gas, t the absolute temperature, y^ the density
of the volatile substance in the gas and a the constant of the law of
Boyle and Charles. Since this last quantity is inversely proportional
to the molecular weight we may set
_A -
~M>
where M denotes the molecular weight, and A an absolute constant
(the constant of the law of Boyle, Charles, and Avogadro), || and write
the equation in the form
At
s, [2]
in which the value of the potential depends explicitly on the mole-
cular weight.
The validity of this equation, it is to be observed, is only limited
by the applicability of the laws of ideal gases to the gaseous phase ;
there is no limitation in regard to the proportion of the substance in
question to the whole liquid mass. Thus at 20° Cent, the equation
may be determined by the potential for water or for alcohol in a
mixture of the two substances in any proportions, since the vapor
of the mixture may be regarded as an ideal gas-mixture. But at
a temperature at which we approach the critical state, the same is
not true without limitation, since the coexistent gaseous phase cannot
be treated as an ideal gas-mixture. At the same temperature how-
ever, if we limit ourselves to cases in which the proportion of water
does not exceed ^ of one per cent., and suppose the density of the
*The object of this chapter is to show the relation of the doctrine of potentials to van't
Hoff ' s Law (what form van't Hoff s Law takes from the standpoint of the potentials) ;
and to the modern theory of dilute solutions as developed by van't Hoff and Arrhenius.
" Equilib. Het. Subs." [this volume], pp. 135-138, 138-144, 164-165, 168-172, 172-184.
t For the definition of this term see p. 93, also pp. 92-96.
Jin some cases a semi-permeable membrane may be necessary. (Enlarge.) (Is the
term coexistent right in this case ?)
§ Definition. (Enlarge. )
7077 A^/ IYYL
II •£— — = A, pv=-:rjAt. Is absolute used correctly ?
420 UNPUBLISHED FRAGMENTS.
water- vapor, y^, to be measured in a space containing only water-
vapor and separated from the liquid by a diaphragm permeable to
water and not to alcohol, then the above equation would probably
be applicable, since then the water-vapor might probably be treated
as an ideal gas. The same would be true (mutatis mutandis) of the
potential for alcohol in a mixture of alcohol and water containing
not more than T\j- of one per cent, of alcohol*
This law, however, which makes the potential in a liquid depend
upon the density of the substance in some other phase is manifestly
not convenient for use. We may get over this difficulty most simply
by the law of Henry according to which the ratio of the densities of
a substance in coexistent liquid and gaseous phases is (in cases to
which the law applies) constant. If y be the density in the liquid
phase and ygas in the gas, we have
ygas = cy, [3]
and by substitution in equation [2] we have
At
u. = f unc (t) + -j-f log cy,
lu
At
or u. = f unc m + -^ log y, [41
' \ / ' I/I O / ' I. J
At
where the function of the temperature has been increased by -^ log c.
With this value of the potential, which is manifestly demonstrated
only to be used so far as the law of Henry applies, in connection with
the general equation (98), [" Equilib. Het. Subs."] viz.,
v v v v
we may calculate the osmotic pressure, etc., etc., as we shall see more
particularly hereafter.
I. Osmotic pressure.
II. Lowering freezing point.
III. Diminishing pressure of other gas.
Ilia. Effect on total pressure.
IIII. Raising boiling point with one pressure.
IHItt. Raising boiling point with two pressures.
V. Interpolation formula for mixtures of liquids.
In fact, when yDt is small, we have approximately
At
•*** •» 4 i T'^D rf\
,» = Atd-?, [5]
*Alao the potentials of water and alcohol in a mixture may be measured in a vertical
tube of sufficient height. [See p. 413.]
t[In the following discussion, D indicates the dissolved substance, or solutum, and 8
the solvent.]
UNPUBLISHED FRAGMENTS. 421
where n^ denotes the number of molecules of the form (D). Hence
we have for the solution
If t is constant, and also JULB, — a condition realized in equilibrium,
when the solution is separated from the pure solvent by a diaphragm
permeable to the solvent but not to the solutum, — the equation
reduces to
v
Whence p-p'=^Yo = At^, [7]
p' being the pressure where yD = 0, i.e., in the pure solvent. Here
At
p —pf is the so-called osmotic pressure, and -^ yD is the pressure as
JxL-Q
calculated* by the laws of Boyle, Charles, and Avogadro for the
solutum in the space occupied by the solution. The equation mani-
festly expresses van't HofF's law.
For a coexistent solid phase of the solvent, with constant pressure,
the general equation gives
0 = r\ dt-\-m% dfa+v At dyD
for the solution, and
for the solid coexistent phase. Here t and JULS have necessarily the
same values in the two equations, and we may suppose the quantity
of one of the phases to be so chosen as to make the values of ras equal
in the two equations. This gives
At
In integrating from yD = 0 to any small value of yD, we may treat
the coefficients of dt and dyD as having the same constant values as
when yD = 0. This gives
-At -0-t
^/ __ *i'\
If we write Qs for — — -^ (the latent heat of melting for the unit
of weight of the solvent), we get
M-— —
~ MV DQsws'
mp
*.__M-Q At2 _WD At2 rg-i
^•^ ^~ L\t — - 7^ -m f -— -ff y-C ) L J
M,
Not experimentally found.
422 UNPUBLISHED FKAGMENTS.
ttigQg is the latent heat of so much of the solvent as occurs in the
solution. (Or make mg = 1.)
Raoult makes A£ oc ^, with exceptions.
M-Q
With a coexistent gaseous phase of the solvent (the solutum being
not volatile), we have for the solution
and for the gaseous phase
dp = y
Here, on account of the coexistence of the phases, p and fa and dp
and djUL8 have the same values. Hence
Say
7s
, o At
dp_Msdyi)
~nf
P 7s ^D
p-P_M8 TD
p ys>
JITD is the molecular weight [of solutum] in solution ;
Ms is the molecular weight [of solvent] in vapor.
But the foregoing equation suggests a generalization which is not
confined to cases in which the law of Henry has been proved. The
letter M in the equation has been defined as the molecular weight of
the substance in the form of gas. Now the molecular weight which
figures in the relation between the potential and the density of a
substance in a liquid would naturally be the molecular weight of the
substance as it exists in the liquid. It is therefore a natural sup-
position suggested by the equation that, in the case where Henry's
law holds good, and consequently eq. [4], the molecular weight of the
solutum is the same in the liquid and in the gaseous phase ; that in
* [p is the vapor pressure of the pure solvent, P that of the solution.]
Assuming that the vapor behaves like an ideal gas, we have ys'=P s.
L_ At
UNPUBLISHED FRAGMENTS. 423
case the law of Henry and eq. [4] do not hold, it may be on account
of a difference in the molecular weight in the gas and the liquid, and
that the eq. [4] may still hold if we give the proper value to M
in that equation, viz., the molecular weight in the liquid.
But as these considerations, although natural, fall somewhat short
of a rigorous demonstration, let us scrutinize the case more carefully.
It is easy to give an a priori demonstration of Henry's law and
equation [4] in cases in which there is only one molecular formula for
the solutum in liquid and in gas, so long as the density both in liquid
and in gas is so small that we may neglect the mutual action of the
molecules of the solutum. In such a case the molecules of the solutum
will be divided between the liquid and the gas in a (sensibly) constant
ratio (the volume of the liquid and gas being kept constant), simply
because every molecule, moving as if there were no others, would
spend the same part of its time in the vapor and in the liquid as if
the others were absent, and the number of the molecules being large,
this would make the division sensibly constant. This proof will
apply in cases in which the law of Henry can hardly be experi-
mentally demonstrated, because the density of the solutum as gas is so
small as to escape our power of measurement. Also in cases in which
a semi-permeable diaphragm is necessary, an arrangement very con-
venient for theoretical demonstrations, but imperfectly realizable in
practice. (Also in cases in [which a] difference of level is necessary,
with or without diaphragm.) But in every case when the law of
Henry is demonstrably untrue for dilute solutions, we may be sure
that there is more than one value of the molecular weight of the
solutum in the phases considered.
This theoretical proof will apply to cases in which experimental
proof is impossible :
(1) When the density in gas is too small to measure.
(2) When the density in gas is too great, either the total density or
the partial. (Diaphragm or vertical column.)
(3) When the liquid (or other phase) is sensitive to pressure and
not in equilibrium with the gas.
Will the various theorems exist in these cases ?
If one or both appear in a larger molecular form, the densities of
yM and yM' * are proportional and
At
hence one equation of form, /% = - log yM proves all.
[7 refers to the liquid, and 7' to the gaseous phase. ]
424 UNPUBLISHED FKAGMENTS.
Let us next consider the case in which the solutum appears with
more than one molecular formula in the liquid or gas or both. Now
there are two cases, that in which the quantities of the substance
with the different molecular formulae are independently variable, and
that in which they are not. In the [first] case there is no question.
If, for example, hydrogen appears with the molecular formula H2
and also in molecules with the molecular formula H20, these are to be
treated as separate substances, and we have the two equations
At ,
lir-logyH2>
and
At
2o = f unc (0 + M-- log 7 H2o ,
and also if free oxygen is present
At
//o2 = f unc (0 + -^- log yo2.
•"*O|
But when the quantities of the substance associated in the different
molecular combinations are not independently variable, then we have
the equation
[13]
which is exact and certain, and the considerations adduced on p. (*),
which are not limited to gases, seem to show that in this case the
equations of the form (t) all continue to subsist, but we have also the
equation of form (J).
It would therefore appear that we may regard the equation
At
as expressing a general law of nature, where the letter M is the
molecular weight corresponding to any molecular combination in the
liquid and y is the density of the matter which has that molecular
formula, provided that the density y is so small that of the molecules
which it represents only a negligible fraction at any time are within
the spheres of each other's attraction. It goes without saying that
the law is approximative, as the last condition can only be satisfied
approximately for any finite value of y. (Need of verification on
account of the unknown M.)
[The author's manuscript for the proposed supplement ends, so far
at least as a connected treatment is concerned, at this point. The
following notes are appended."]
* [Although left blank in the MS., this probably refers to p. 423.]
t [Probably equation [ 12]. ] J [Probably equation [13]. ]
UNPUBLISHED FKAGMENTS. 425
In case of one molecular formula in liquid and none in gas, we
may give the molecules repelling forces which will make the gas
possible. (?) [See p. 417.]
Deduce Ostwald's law in more general form.
Deduce interpolation formula.
What use can we make of Latent Differences? //A, /ZAA, /ZB, yuBB,
/XAB all conform to law, I think.
[On the Equations of Electric Motion.]
[A somewhat abbreviated copy of a letter written four years earlier
(in May 1899) to Professor W. D. Bancroft of Cornell University Jwd
been placed by Professor Gibbs between the pages of the manuscript,
and was evidently intended to serve as a basis for the chapter " On
the equations of electric motion " mentioned in the list on page 418.
Through the courtesy of Professor Bancroft the original letter has
been placed at the disposal of the editors and is here given in full.
The major portion of this letter was incorporated by Professor
Bancroft in an article entitled " Chemical Potential and Electro-
motive Force" published after the death of Professor Gibbs, in the
Journal of Physical Chemistry, vol. vii.,p. 416, June 1903.]
My dear Prof. Bancroft :
A working theory of galvanic cells requires (as you
suggest) that we should be able to evaluate the (intrinsic or chemical)
potentials involved, and your formula
is all right as you interpret it. I should perhaps prefer to write
At
logyD, (1)
At
or yvdp^dyv, (2)
for small values of yD, where yD is the density of a component (say
the mass of the solutum divided by the volume of the solution), M^ its
molecular weight (viz., for the kind of molecule which actually exists
(1DV A \
t~MJ' an(* ^ a
quantity which depends upon the solvent and the solutum, as well as
the temperature, but which may be regarded as independent of yD so
long as this is small, and which is practically independent of the
pressure in ordinary cases.
426 UNPUBLISHED FRAGMENTS.
We may avoid ' hedging ' in regard to B by using the differential
equation (2). We may simply say that this equation holds for
changes produced by varying the quantity of (D), when yD is small.
It is not limited to changes in which t is constant, for the change
in fiD due to t appearing in (1) (both explicitly, and implicitly in B)
becomes negligible when multiplied by the small quantity yj>.
The formula contains the molecular weight JfD, and if all the
solutum has not the same molecular formula, the yD must be under-
stood as relating only to a single kind of molecule.
Thus if a salt (12) is partly dissociated into the ions Q and (2),
we will have the three equations
The three potentials are also connected by the relation
which determines the amount of dissociation. We have, namely,
M.B. + M2B2 - MIZB12 + ^ log 2 = 0,
7l2
which makes constant, for constant temperature and solvent.
Vl2
I may observe in passing that this relation, eq. (1) or (2),
which is so fundamental in the modern theory of solutions, is some-
what vaguely indicated in my " Equilib. Het. Subs." (See [this volume]
pp. 135-138, 156, and 164-165.) I say vaguely, because the coefficient
of the logarithm is only given (in the general case) as constant for a
given solvent and temperature. The generalization that this coefficient
is in all cases of exactly the same form as for gases, even to the details
which arise in cases of dissociation, is due to van't Hoff in connection
with Arrhenius, who suggested that the " discords " are but " harmonies
not understood," and that exceptions vanish when we use the true
molecular weights. At all events, eq. (2) with (98) (E.H.S.) gives for
a solvent (S) with one dissolved substance (D),
m , At
If we integrate, keeping t constant and also ju.8 (by connection with
the pure solvent through a semi-permeable diaphragm), we have van't
HofTs Law,
, At
UNPUBLISHED FRAGMENTS. 427
In the above case of dissociation the formula would be
For a coexistent solid phase of the solvent we have for constant
pressure
At
ms being for convenience taken the same in both phases.
Then
In integrating for small values of yD we may treat the coefficients
of dt and cfyD as constant. This gives
— rt'\
or if we write Q8 for — — — (the latent heat of melting for the unit
7/lg
of weight of the solvent), we have
This may be written
-A*-™8*0 At*
M8 Q8M8
According to Raoult, the first member of this equation has a value
nearly identical for all solvents and solutes (supposed definite com-
pounds). This would make the second member the same for all
liquids of " definite " composition, when we give MB the value for the
molecule in the liquid state. I should think it more likely that these
properties should hold for the two members of the equation
A£ ms MI>_ At
"
which are pure numbers (of no dimensions in physical units). In
this form it has a certain analogy with van der Waals' law of
" corresponding states."
With a coexistent vapor phase of the solvent, we have
At
-T- Tf-
v— v MD
428 UNPUBLISHED FRAGMENTS.
We may regard -^- - as constant in integrating (for small yD), which
i/ ~* i
gives p_ _^ AfyD
-P-J-vAtM»
At At PMS
Now -r- - = ,7 = - ! nearly, which gives
v — u HU
is Raoult>s Law<
m
Raoult found values about 5 per cent, larger than this, which agrees
At PM
very well with the fact that - - is somewhat larger than - — . It
*y ~~ i) fft'
is also to be observed that MD relates to the molecules in the solution,
but M8 to the molecules -in the vapor. Or, with a coexistent vapor
phase of the solutum (alone or mixed with other vapors or gases),
we have
41
M-Q
At
B-BM
~ATM»'~
* -*•-
which makes 23L constant for the same solvent, solutum, and tern-
YD
perature, according to Henry's Law.
So for the galvanic cell which you first consider, I should write
V -V' = a.(ff - /) = «. log ,
1VLa ya
ya> ya being the densities, supposed small, of the cation (a) in the two
electrodes, which are supposed identical except for the dissolved (a).
Here aa has reference to the solution and Ma to the electrodes. It
may be more convenient to divide aa into the factors Ea, aH, where
aH is the weight of hydrogen which carries the unit of electricity, and
Ea the weight of (a) which carries the same quantity of electricity as
the unit of weight of hydrogen. In other words Ea is Faraday's
" electrochemical equivalent " and aa is Maxwell's " electrochemical
equivalent." This gives
M
where anA is your R and -~ your v, v'*
* [The valence of the ion].
UNPUBLISHED FRAGMENTS. 429
The meagreness of the results obtained in my E.H.S. in the matter
of electrolysis has a deeper reason than the difficulty of the evaluation
of the potentials.
In the first place, cases of true equilibrium (even for open circuit)
are quite exceptional. Thus the single case of unequal concentration
of the electrolyte cannot be one of equilibrium since the process of
diffusion cannot be stopped. Cases in which equilibrium does not
subsist were formally excluded by my subject, and indeed could not
be satisfactorily treated without the introduction of new ideas quite
foreign to those necessary for the treatment of equilibrium.
Again, the consideration of the electrical potential in the electrolyte,
and especially the consideration of the difference of potential in
electrolyte and electrode, involves the consideration of quantities of
which we have no apparent means of physical measurement, while
the difference of potential in "pieces of metal of the same kind
attached to the electrodes" is exactly one of the things which we" can
and do measure.
Nevertheless, with some hedging in regard to the definition of the
electrical potential, we may apply
V*-Vf = aa(pa'-pS)
to points in electrolyte (') and electrode (").
This gives
say, rvr
The G like the P of your formula seems to depend on the solvent,
presumably varies with the temperature, but as Nernst remarks does
not depend on the other ion associated with (a), so long as the solution
is dilute.
The case of unequal concentration, or, in general, cases in which
the electrolyte is not homogeneous, I should treat as follows ; Let us
suppose for convenience that the cell is in form of a rectangular
parallelepiped with edge parallel to axis of x and cross section of unit
area. The electrolyte is supposed homogeneous in planes parallel to
the ends, which are formed by the electrodes.
Of course we should have equilibrium if proper forces could be
applied to prevent the migration of the ions and also of the part of
the solutum which is not dissociated. What would these forces be ?
For the molecules (12) which are not dissociated, the force per unit of
mass would be C^. (The problem is practically the same as that
CttK/
discussed in E.H.S. [this volume], pp. 144 ff.) If the unit of mass of
430 UNPUBLISHED FRAGMENTS.
the cation d) has the charge clt the force necessary to prevent its
migration would be
d/UL, , dV
' •*• — L yi ..__,_,
dx 1 dx'
For an anion (2) the force would be
dx 2 dx'
Now we may suppose that the same ion in different parts of a
dilute solution will have velocities proportional to the forces which
would be required to prevent its motion. We may therefore write
for the velocity of the cation (l),
, dV
"H C*
and for the flux of the cation (1),
~ , - .--- —
7l 7l \~fa °l dx ' - C.M, dx dx
for the flux of the anion (2),
dV
,..
where kly k2 are constants ('migration velocities') depending on the
solvent, the temperature, and the ion.t Now whatever the number
of ions the flux of electricity is given by the equation
where the upper sign is for cations and the lower for anions, and the
summation for all ions. This gives
That is, J
2HFi
A 1Y* , T_
-At l dV.
/y /yi
The form of this equation shows that since 0 is the current,
is the "resistance" of an elementary slice of the cell, and the next
term the (internal) electromotive force of that slice.
* [c, is a positive number equal numerically to the negative charge on unit mass of
the anion.]
t[The positive direction for both these fluxes is the direction of increasing x.]
t [The sign of the charge is not included in c. Honce the double sign is necessary.]
UNPUBLISHED FRAGMENTS. 431
Integrating from one point to another in the electrolyte,
Cl/C1yl
The evaluation of these integrals which denote the resistance and
electromotive force for a finite part of the electrolyte depends on
the distribution of the ions in the cell. For one salt with varying
concentration,
dx
or, since C1y1 = c2y2 and C1c?y1 = c2(iy2,
I-
™\
dx
Vl
i ^2
The resistance depends on the concentration throughout the part of
the cell considered, but the electromotive force depends only on the
concentration at the terminal points (' and ").
/y <y
For C1M1 and czM2 we may write — and -1, where vl and vz are
an an
the " valencies " of the molecules. This gives
2i _ ^2
V"- V7 = aHAt-~zlog^jf, for 0 = 0 (circuit open).
I think this is identical with your equation (V) when your ions
have the same valency.
Planck's problem is less simple.* We may regard it as relating to a
tube connecting the two great reservoirs filled with different electro-
lytes of same concentration, i.e., ^oyo' = 20Coyo"' I use (o) f°r any
ion, (J for any cation, (2) for any anion. [The accents Q and (")
refer to the two reservoirs.]
The tube is supposed to have reached a stationary state and
dissociation is complete. The number of ions is immaterial, but they
all must have the same valency v.
v
Now by equations (3) and (4), since cJJ/0 = — ,
«H
dV
[Planck, Wied. Ann., vol. xl (1890), p. 561.]
432 UNPUBLISHED FRAGMENTS.
or, writing T for the constant
(to
[The terms ^f -s— c0y0 disappear in the algebraic sum since
a similar reason]
The first equation makes — j-2^ constant throughout the tube, and
since SoCoyo'' = 20c0y0', 2c0y0 must be constant throughout the tube.
The second equation then makes -=— constant throughout the tube.
T L V
Let -i =
Our original equation is
Now with ^ constant this is easily integrated.
"0
To determine H0 we have
y0"-y0' = £0ve - -e
If we put the origin of coordinates in the middle of the tube
we have
UNPUBLISHED FRAGMENTS. 433
T i. T"> T
I 4 »t r^ ••• 0
Ijct i — t >
Let A0 = y0//-y0/,
C/A P
OV^O i 7 A
0 OyO"' V "~ -^ (X^O 0 L> D— 1 *
^1 JT — ±
The condition of no electrical current gives
±~x
e T
Apply to both ends and add,
±*"
P+P'1
= o coo^o p _ p-i '
If we set, to abridge,
When the summations are for cations or anions separately, the
last equation may be written
which gives P2 =
Now
^ is the part of the conductivity of the first electrolyte which is
due to the cations.
If the first electrolyte contains only one cation Q and one anion (2),
and the second only one cation (3) and one anion (4), we have
or, since Cly/ = C2y2' = C8y8" = C4y4",
r,_Fs=1
v tok
like the formula which you quote.
G.I. 2E
434 UNPUBLISHED FRAGMENTS.
I regret that I have been obliged to delay my writing so long. I
presume that you would have preferred to have me reply more
promptly and more briefly. But the matter did not seem to be
capable of being dispatched in few words.
One might easily economize in letters in the formulae by referring
densities (y) and potentials (JUL) to equivalent or molecular weights, as
you have done, but I thought I was more sure to be understood with
the notations which I have used. Moreover, since the molecular
weight is often the doubtful point in the whole problem, there is a
certain advantage in bringing it in explicitly rather than implicitly,
so that we can see at a glance how a change in our assumptions in
regard to the molecules will affect the measurable quantities.
Yours, very sincerely,
J. WILLAKD GIBBS.
0
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