CONNECTICUT ACADEMY
OF
VOX^XJJVIE III
t7>
NEW
1874
TulUr, Murehouse
AYEN
New Ha
CONTENTS.
PAGE
v
St.
Art.
I.
Report
on the dredgings
in
S.
the region of
I.
By
Smith and O.
1
H arger.
Plates
8,
op
species of Hy
NeW EnGLAND
COAST.
By
S.
F,
Clark.
Art.
III.
Plates 910,
58
TillyFoster
Dana,
Plates
67
Art. IV.
sin
ic
On the Transcendental curves sin y sin iny=. By II. A. Newton and A. W. sin ??a; ^''
Philips.
Plates 1437,
equilibrium of heterogeneous sub
97
Art.
V.
On the
stances.
Art. VI.
By J. W. Gibbs. First Part, The Hydroids of the Pacific coast of the United States south of Vancouver Island, with a report upon those in the Museum of Yale Coixege.
108
By
By
S.
F. Clark.
Plates 3841,
habits of Nereis virens.
249
Art. VII.
Y.
Plates 4244,
fins, a contribution to
265
Art. VIII.
limbs.
By
J.
K. Thacher,
281
Early stages op Hippa talpoida, with a note ON THE structure OF THE MANDIBLES AND MAXILLJE IN Hipp A and Remipes. By S. I. Smith. Plates 4548, 311 Art. X. On the equilibrium op heterogeneous sub
stances (concluded).
By
J.
W.
Gibbs,
343
President,
ELIAS LOOMIS.
VicePresident,
HUBERT
A.
NEWTON.
/Secretary,
OSCAR HARGER.
Librarian,
Treasurer,
HENRY
C.
KINGSLEY.
PtihlisJdng Committee,
HUBERT GEORGE
CHESTER
A.
J.
S.
NEWTON,
BRUSH,
LYMAN,
ADDISON WILLIAM
WHITNEY.
Auditiiig Committee,
HUBERT
A.
NEWTON,
DANIEL
BLAKE.
C.
EATON,
HENRY
T.
Maximum zu."
CLAfsitrs.*
The comprehension
is
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 combined 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
greatly facilitated
is
entropy
the limit of
all
/
,
[dQ denoting
and
t
the
is
that
by the system
in
For by mechanical and theiTuodynamic conany 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
to
another.
trivances, supposed
theoretically perfect,
But
it
is
its
ai'e
of
predominant importance.
As
in the case of
system, (such as
all
is
capable of
two
ix., S.
44.
J.
W. Gihhs
109
The
from
isohited
all
external influences
may
For
the equilibrium
it
is
and
of the state of the system which do not alter its energy, the va.riatio7i of its entropy shall either vanish or be negative. If a denote the energy, and // 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
{^V)e ^0.
(1)
it is
II.
For
the equilibrium
necessary
and
the state
of
the system
which do not
of
its
vanish or be positive.
This condition
may
be written
(2)
m,=
sideration that
it
0.
appear from the conalways possible to increase both the energy and
will
viz.,
by
it
away.
For,
condition (1)
is
state of the
>
and 6e
=0;
therefore,
system in
by diminishing both the energy and the entropy of the its varied state, we shall obtain a state for which (considered
from the original
state)
as a variation
not satisfied.
Conversely,
if
condition (2)
for
which
d<
and St/z^ 0;
de=iO and
therefore condition (1)
is
(J//
>
not
satisfied.
of equilibrium, as also
in
infinitesimals
110
tf.
Substances.
relatively to tliose
are to be neglected.
we
will
variations.
We
strued strictly,
e.,
in
this understanding, we may express the necessary and sufficient conditions of the different kinds of equilibrium as follows; for stable equilil)rium
not to be neglected.
With
(^;/),<0,
for neutral equilibrium there
i.
e.,
(A6),^>0:
in
(3)
the state of
e., {Af),^
0,
(4)
while in general
{^V)e ^0,
i.e.,
(Af),^^0;
for
(5)
and
which
(6)
(A;/),>0,
i.
e.,
there must be
some
for
which
(^f),<0,
while in general
(V)
(d7),^0,i.e., (c^f),^0.
(8)
is
taken only
tliis is
In the
any
finite
although they
may
if
tions of quantities
For example,
its
not to
In
resist
But,
if
will
be neces
J.
W. Gihhs
Ill
these parts, as sueli a change can not take place without the passage
This limitation may most conveniently l>e aiplied to the second of the above forms of the condition of equilibrium, which will
of heat.
then become
there
is
no communication of heat.
When
conduction
no farther consideration.
requisite of its passive forces or
is
(Those passive forces which only retard change, Such properties of a system like viscosity, need not be considered.)
aie in
of
its
friction
As examples, we may instance the passive force of which prevents sliding when two surfaces of solids are
pressed together,
that which
from another,
from having different motions one 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
a solid, and sometimes of a
fluid,
that
resistance to change
of
and heat which allow finite variations in the values of all the quantities which express the initial state of the system or the mechanical or thermal influences acting on it, without producing the change in The equilibiium which is due to such passive properties question.
limits
is
may be modified, and to whatever external agencies of force it may be subjected, within limits, it may be, but yet within
by the balance
of the
where an external influence, or a change in the initial state, infinitesimal in amount, is sufficient to produce change either in the positive or negative direction. Hence the Only in ease with which these passive resistances are recognized. the case that the state of the system lies so near the limit at which
the resistances cease to be operative to ])revent change, as to create a
112
J.
W. Gihhs
To
we
will
consider
two equivalent
forms.
its
In the
first
place,
if
the system
is in
a state in which
entropy
is
it is
evidently in
must involve
either a decrease of
iso
no
change of
increase of energy.
We
with
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
;
difierent
components
in diiferent
Avhen
the
momenta
of the components
Nor,
of heat take place, for this involves an increase of entropy, as heat equally impossible that any changes should
transfer of heat
by
radiation.
posed
is
masses and the transfer of heat are concerned, but to show that the same is true in regard to the motions of difiiision and chemical or
molecular changes, when these can occur without being accompanied
or followed
by the motions
we must
have recourse to considerations of a more general nature. The following 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.
J.
W. Gibhs
113
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 constate of the
in
in nature
This time must be so chosen that the change does not take place in
which
is
pose to take place cannot be infinitely slow except at particular moments. Now no change whatever in the state of the system,
w^hich does not alter the value of the energy,
in
and which commences which the system was supposed at the com
mencement of the
entropy.
short time considered, will cause an increase of Hence, it will generally be possible by some slight varia
make
all
changes
in the state
is
supposed actually to
be in the values of the variables which determine the state of the system, or in the values of the constants which determine the nature of the system, or in the form of the functions which express its laws, only there must be nothing in tbe system as modiThis variation
may
fied
which
is
thermodynamically impossible.
if
we
is
then, there
it is
any tendency toward change in the system as tendency which can be entirely checked by an
in
first
supposed,
infinitesimal variation
As
be
allowed,
we must when
in
always in equilibrium
its
when
it
energy, or, in
its
other words,
entropy.
0,
even
if
the entropy
(The term possible has here the meaning pieviously defined, and the character A is used, as before, to denote that the equations are to be
Trans. Conn. Acad., Vol.
III.
15
October, 1875.
114
ff.
W. Gibbs
construed
sti'ictly,
e.,
higher orders.)
The only
in
that in which
our notation
6ij
when
the
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 But the differential coefficients of all orders of (Jz/p^O holds true. the quantities which determine the state of the system, taken with respect of the time, must be functions of these same quantities. None of these differential coefficients can have any value other than For otherwise, as 0, for the state of the system for which dr]^ ^ 0. be possible, before, infinitely small would generally as some it by 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 differential coefficients which had before the finite values, or in some of lower orders, Avhich is contrary to that continuity which we have reason to expect. Such considerations seem to justify us
entropy has
in
in
we
equilibrium
evidently unstable,
it
cannot be realized.
We
have
still
is
in
every
evidently so in
all
cases in
statement of
(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
state of equilibrium
((J;/),
0,
i.e.,
(rJ6),
=
is
(10) in every
But
previously enunciated
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 infinitesimal part) of its matter, which would diminish its energy by a
case necessary,
J. TF,
Gihhs
is
EqtiiUhrinm
or,
of Heterogeneons Svhstwtces.
115
quantity which
altering
entropy,
if
without
altering
the
entroi)y
this
variation
its
passive
Now,
as the described
its
energy without
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 Hence we may conclude that the active forces or tendensystem). cies of the system favor the variation in question, and that equilibrium cannot subsist unless the variation is prevented by passive
forces.
will suffice,
it is
believed, to establish
The
criteria of stability
may
librium.
We
will
now proceed
systems
which
it
of phenomena.
For
this
purpose we
admits more readily the introduction of the condition that there no tliermal communication between the different parts of the it is more convenient, as respects the form of
shall be
make
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
we
our
We will
mass of matter of various kinds enclosed and fixed envelop, which is impermeable to and unalterable by any of the substances enclosed," and perfectly nonconducting
to heat.
We
will
is
action of gravity, or
solid portions of the
by any
electrical influences,
is
and that
in
the
116
J.
Substances.
problem by supposing that the variaand 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
will farther simplify the
We
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 nonconducting envelop enclosing the mass under discussion involves no
real loss of generality, for if
would
also
be
so, if
any mass of matter is in equilibrium, it the whole or any part of it were enclosed in an
;
envelop as supposed
mass thus enclosed are the general conditions which must always
be satisfied
in
case of equilibrium.
all
As
for the
other suppositions
the circumstances
and considerations
the
subject
will
afterward be
made
of
Conditions relating
to the Equilihr'nim
Homogeneous Parts of
Let us
first'
the given
Mass.
any possible variation in the com(By homogeneous is meant that the uniform throughput, not only in chemical comphysical state.) If we consider the amount and
variation for
its
energy
f is
entropy
7/,
and
its
volume
y,
and the
differentials
de
t
dt]
J) dv,
p
its
(1 1)
pressure.
For
*
the heat received, and p dv the work done, by the mass change of state. But if we consider the matter in the m for the quantities of the mass as variable, and write mj, mg, S^ of which the mass is composed, e various substances aS,, S2, will evidently be a function of ?;, w, my, ni^, ?, and we shall
dn
is
during
its
differential of e
\ yw^ ^^'"2
de^itdi]
y^ J,
+/^"
^^'"n?
(1)
7^2 5
/'n
taken with
?w.
The substances
aS^,,
S21
J.
W. Gihbs
dm2,
.
llV
tials d'm^,
dm
shall
from any
initially present.
may
to
therefore be necessary
relating
component substances
which do not
to be found in
initially
some part of the whole given mass. mentioned are satisfied, the choice of the substances which we are to regard as the components of the mass considered, 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 fi'ee hydrogen and oxygen, we should be obliged to recognize three components 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 (addiIf the conditions tional) water.
If,
state of
maximum
however, we are considering sulphuric acid in a concentration in connection with substances which
might possibly
affoi'd
water to the
acid, it
we
maximum
this
concentration as one of
will then be capa
the components.
The quantity of
component
in
in the positive
and
the quantity of the other component can increase but cannot decrease
0.
For brevity's sake, we may call a substance S,, an actucd component of any homogeneous mass, to denote that the quantity m of that substance in the given mass may be either increased or diminished (although we may have so chosen the other component substances that rn^ and we may call a substance S,, a jiossible component 0) to denote that it may be combined with, but cannot be substracted from the homogeneous mass in question. In this case, as we have seen in the above example, we must so choose the component substances that W4 =z 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
118
all
J.
W. Gihhs
may be more
It
may be
observed that
it
is
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 homogeneity, provided that in all parts of the mass the variations of
nature and state are infinitely small.
For,
if this last
condition be
all
is
the infin
i.
e., if
we write
infinitesimal part,
f //
cWn
clD)}
 p dlJv
dDm^\
fx,
cWni^
clDm^,
(13)
(12)
by integrating
is
for the
whole
We
will
now suppose
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
We
,
neous, and together occupying the whole space within the envelop. 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 If we aS being an actual component of each part. S'2, /S
.
by
accents,
the variation in the energy of the system may be expressed by ^f __ (Jf" _j etc., and the general condition of equilibrium requires
'
that
Se' _
ds"
etc.
(14)
which do not
of condi
These equations must express that the entropy of the whole tion. given mass does not vary, nor its volume, nor the total quantities of will suppose that there aS. any of the substances >S\, /6'g,
. . .
We
It will
equilibrium that
t'
Sr,'
2^'^v' +///(ym,'
\
juj 6rn,J
/A2"
.+//'
.
(Jm'
__ t"
S7/"
6m,"
//,."
6m ^'
(15)
f
etc.
^
which
for
+ (J7" 4
(5/7'"
etc.
0,
(16) (17)
^'j^Svnj^Sv"'\
etc.
=0,
J.
W. Gibbs
119
(^m/
dm.^'
Sm^"
dni.^"
+
\
+ dm^'" + + Sni^'" +
j
etc.
etc.
= =
0.
0, 0,
I
/jg\
and
dm^'
Si/i"
(ym"'
\ etc.
=r
For
this
it is
= = t"'=
t"
etc.
(19)
jj
yu
=ip" =p"'
'
yU
J
etc.
'"
(20)
etc.
"]
A<2'
//,/
"
^21)
J
/u"'
etc.
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 have the conditions characteristic of chemical equilibrium.
call
(21)
If
we we
a quantity
//,,
as defined
by such an equation as (12), the potential homogeneous mass considered, these conbe
ditions
may be
expressed as follows
TTie potential
constant
It will
restriction
The
state of the
(if
we
of the quantities of which the variations occur in (15). of these quantities, which
The number
is
we may
is
call the
independent variables,
number of homogeneous
All
parts
divided.
may be
as
if
is
known
its
com
ponents.
may
be I'egarded as {y \) [n { 2) independent equations between the independent variables. The volume of the whole mass and the total
quantities of the various substances being
tional equations.
If
known
aiford n\
addi
we
also
know
will
mass, or
its total
entropy,
we
120
tT
W. Gibbs
S^ are only possible comany of the substances ^S'j, 8^ ponents of some parts of the given mass, the variation 6m of the quantity of such a substance in such a part cannot have a negative
But
if
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 In this is an actual component, but only that it shall not be less.
case instead of (21)
we may
S^i
write
which
is
which S^
is
ponent,
/'2
^^2
(22)
which S^
is
which S2
is
Donent,
J/j, J/2? ^^^5 clenoting constants of which the value
is
only deter
we now suppose
various homogeneous parts of the given mass are not the same, the
result will
different
be of the same character as before, provided that all the components are independent., (i. e., that no one can be made out of the others,) so that the total quantity of each component is The general condition of equilibrium (15) and the equations fixed.
of condition (16), (17), (18)
will require no change, except that, if
.
/S'j,
S^
is
any
part, the
term
//
be wanting
and the Sin in the latter. This will require form of the particular conditions of equilibrium as no change expressed by (19), (20), (22); but the number of single conditions contained in (22) is of course less than if all the component subWhenever, therefore, each stances were components of all the parts
in the former, in the
may
be regarded
composed of some or of
all
of the same
set of substances,
is
may be
expressed as follows:
J.
W. Gibhs
121
The potential for each of the component substances must have a j)'irts of the gioen mass of which that substance is an actual component, and have a, value not less than this in all parts of ^ohich it is a jtossible comjjonent. The number of equations aiForcled by these conditioiiH, after elimination of iJfj, J/2, J/, will be less than {n + 2) (k  1) by the number of terms in (15) in which the variation of the form 6rn is either The number of necessarily nothinij or incapable of a negative value. variables to be determined is diminished by the same number, or, if
constant value in all
. .
.
we
choose,
we may
]>ut
m=
is
for each of
these terms.
show whether the supposition that the substance component is consistent with equilibrium.
not an actual
We will
all
now suppose
*S\, aSj,
6'
are not
e.,
that some of
out of others.
We
be
composed of S^ and
combined
in
the ratio of a to
b,
S^ and S^
occurring as actual components in some parts of the given mass, and /iS'g in other parts, which do not contain S^ and 82 as separately
variable
still
IX
components.
The general
condition
of equilibrium
will
have the form of (15) with certain of the terms of the form
omitted.
It
6m
may
[(23)
:^'{t6if)
:^{pSv)\:^{/J,dm^)\^{;i2d^m.,).
.^2:{/./drn)^0,
of condition,
0,
2 dm = 0, 2 6m = 0,
2
:2 6m ^
(24)
we
shall
122
J.
W.
(jrlbbs
For, although
yet
it
it
may
6m
^'
is
tive value.
(23)
(2;3)
must
Again,
if
is satisfied,
must
which
in all the parts of of the quantity of every substance has the value But as this limitation does not it is not an actual component.
afiect the
it
may
drn^, and '2 6m^, 6m^, range of the possible values of be disregarded. Therefore the conditions (23) and (27) are
when (19), (20), (22) are satisfied. Now, by means of the equations of condition (25), we may eliminate :^ dm^ and 2 6ni2 from (27), which becomes
entirely equivalent,
{a
0,
(28)
e.,
as the value of
^
a
6m^ may
M^ ^bM^
{a + b) M^,
is
(29)
which
is
necessary
in this case.
The
relations
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 difiiculty, i^nd will enable us to eliminate from the general condition of
equilibrium as
after
many
which the
coefficients of the
remaining variations
may be
set
equal to zero, except the eoefiicients of variations which are incapable of negative values, which coefficients must be equal to or greater
than zero.
It will
it
may
be easy to perform these operations in each parbe inteiesting to see the form of the resultant
equations in general.
homogeneous parts
S^,
.
are considered
is
/S,
no
freedom of motion and combination. But we generality of the problem as to suppose that the limit far so will is an actual component of some part of components these of each of these components can be formed out of some If mass.* the given
upon
their
by equations such
etc.
as
(30)
a(Ba+P ;, +
where a,
*
(Sj, i, etc.
<^tc.
=:
7c
3,
+ A @, +
S^,, Sf,,
etc.,
When we come
we
shall take
and give
it
J.
Sitbstances.
123
fi,
;(,
(that
etc.
is,
S ^,
it
So,
f^,)
and
<(,
denote nnmhers.
will
be observed, equations
denotes qualitative as
We
The equations
of con
relating to the
easily be derived
will not
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
(2.3)
will
reduce to
. . .
J/j
^ 6m + 3I2 2 Sin,^
J
\
JI
2 (hn^
0.
(31)
This will appear from the same considerations which were used in
(27).
etc.
Now
it
is
evidently possible to
/J,
2 Srn^, 2
2 Sm =^
a 31^
Snii,^
2 dm^.,
values proportional to a,
n,
in equation (30), in
making
therefore
31,,
or,
0,
(32)
(33)
coeffi
It will
be observed that
this equation
31 taking the
It is evident that
which (30) is an example, which may be obtained simWhen these condiply by changing in these equations into 3f. any possible values of tions are satisfied, (31) will be satisfied with 2 6111^. For no values of these quantities are Sdm^, 2 Sm^,
r equations of
.
.
{2 6m ,)(^,
tions like (30),
+ {2 6m.,) ^
+ (^' 6m,) =
from the
r
(34)
equa
by the ordinary
Therefore, on account of the correspondence between (31) and between the r equations like (33) and the r equations like (30), tiie conditions obtained by giving any possible values to the variations in (31) may also be derived from the r equations like
equations.
and
(34),
(33)
(33)
(19),
that
are
is,
is
satisfied, if the
equations like
Therefore the r equations like (33) are with (20), and (22) the equivalent of the general condition (15)
satisfied.
or (23).
124
J.
^Substances.
For
mass when
in
equilibrium
and having
matter
in
ti component subBut the equations which express our knowledge of the the given mass will be correspondingly diminished, being
r in
number,
like
quantities of the
the former
by
differentiation.
to tlie possible Jb^ormation
Conditions relating
Previoush/ Existing.
The
variations which
we have
sufficient.
may be
formed entirely
and composition from any initially Such parts of the whole mass in its varied state as existing. cannot be regarded as parts of the initially existing mass which have been infinitesimally varied in state and composition, we will These will necessarily be infinitely small. As it is call nev) parts.
different in state
more convenient to
I'egard a
vacuum
mation of empty spaces within the given mass, the term new parts
will
empty spaces which may be formed, We will use De, Dr], Dv, Dm^, D}n to denote the infinitesimal energy, entropy, and volDm^, ume of any one of these new parts, and the infinitesimal quantities The component substances /S\, Sg, S must of its components.
be used to include
anj^
existed initially.
now be taken
to include
components of
the
formation of which
we have
to consider.
used as before to express the infinitesimal variations of the quantities which are only infinitesimally varied in state
for distinction
we
such exist
initially,
As we may
divide the
many
parts as
we
J.
W. Gibhs
125
initial
any variation
we may
so
them
as initially
we have called original, that we may consider homogeneous and remaining so, and as initially conof
the
is
:^6\:^D,
the
first
(35)
summation
relating to
all
to all the
letter
new
parts.
6 or
D following ^ will
(Throughout the discussion of this pi'oblem, the surticiently indicate whether the sumparts.)
Therefore the
:2de>[or, if
:^6e^0,
(36)
[(^V) we substitute the value of 6e taken from equation (12), 2De+^{txhj)  2{pr3v) + 2U.i,6, ,)+^{i,^6w.,) +2{i<^hn:)^ 0.
.
.
If
S ^,
S^^
*S'
we
page
122), that
Let these be
^1
i
etc.
^2
^>n
I r equations.
)
(38)
The equations of condition will be (if there is no restriction upon the freedom of motion and composition of the components)
2 di] f 2 By = 0, 2 Sv + ^ Dv 0,
z=z
(39) (40)
and n
r equations of
h^
tj
the form
jh^
{^dm^ + ^Dm^)
{2Sm, +2Dm.^)
etc.
+
+i.^
{^(hn^ + {2 Sm
^ Dm^
+
JS"
1
j
I)m)
.
=
.
{^dm +
{2 Sm
f /
2 JDm^J + 2 1)m) =
(41)
(41)^
coefficients in
and those in
(38),
the
the coefficients of any one of equations (41) are such as would satisfy aU the equations (38) if substituted for S,, S.^, S and
.
.
that this
is
the only condition which these coefficients must satisfy, except that the
be independent,
i.
e.,
shall
pendent equations
equations
is
and that
this relation
between the
coefficients of the
two
sets of
a reciprocal one.
126
J.
W. Gibhs
Now,
tract
using Lagrange's
{^^ di]
[
we
iirst
will sub
21)!/)
P{2 6v + 2 D)j)
from the
member
yand
P being constants
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
{2 6m^
f
(42)
for
of the letters i, 'B^, were substituted their values in terms of the others as derived from equa
tions (38).
ties,
(Although
(5
J,
2,
satisfy
let
3f
0,
f *
M =
0, 1 r
)
equations, (43)
then
This
.
. .
{^dm^^^Bm^) + J/ {2 Sm + 2 Dm,,) = 0. (44) r of the constants M^, M2, expression, in which the values of
J/,
{2 6m^r2I)m^) + M2
11
are
still
arbitrary,
we
from the
first
mem
become
{]>
+ 2 (yM (hn) + M 2 6m
^3I2Dm>.0.
..
(45)
That
is,
having assigned to
T,
P, 31^, J/2,
it is
we may
assert that
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,
iHfg,
. .
3f,
On
in (3T),
of negative values, the successive steps in the reasoning will be developed at greater
J.
W. Gihhs
127
and in the quantities of the various substances composing it, even though these variations are not consistent with the equations of conFor, when it is not possible to do this, it dition (39), (40), (41). must be possible by applying (45) to variations in the system not necessarily restricted by the equations of condition (39), (40), (41) to M, some of obtain conditions in regard to 1\ P, Jf,, M2, which will be inconsistent with others or with equations (43). These
. . .
conditions
we
will represent
by
.4^0,
^^0,
etc.,
. .
(46)
Then it A, B^ etc. being linear functions of T, P, 31 1, J/g, 31,. will be possible to deduce from these conditions a single condition of the form
aA+/3B+
etc,
0,
(47)
a,
/3,
etc.
being positive constants, which cannot hold true consistBut it is evident from the form of (47)
(46), it
directly
from
by applying
this
by
Now
evident, in the
place, that
it
cannot contain
T or
fore in the
change
in the
(for
P, therewhich (45)
reduces to (47))
2 d?f + :^ 1)1} = 0,
for the
and
:^
60
+ :2 Bv = 0,
Again,
same reason, the homogeneous function of the first degree of iHfj, Jfg, 3f in (47) must be one of Avhich 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
.
. .
2 dm + 2 Bm ,).,+
1
(>;
dm
(
, f li'
{
X>>/i,
31^
+ 2 dm 2 Bm) 3/ ~
for
(48)
3f
which
satisfy
eqs.
(43),
and
therefore
{2^Smj
+ 2 Bm^)
(49)
for
(S^, ^2, which satisfy eqs. (38). This equation (4D) will therefore hold true, if for r of the letters
(S
Bn we substitute
will
we
use
128
J.
W. Gibbs
.
Equilibrium
of Heterogeneous Substances.
J,
(2 2,
ponents.
The change in the system, there(41). which we are considering, is not one which viohites any of the equations of condition, and as (45) does not hokl true for this change, and for all values of T, P, M^, M.^, M^ which are consistent with eqs, (43), the state of the system cannot be one of equilibrium.
the equations of condition
fore,
.
Therefore
that
it
it is
necessary, and
it is
shall
be possible to assign to
in the
P, 31^, J/gi
consistent with eqs. (43), that the condition (45) shall hold true for
any change
For
this
it is
t=l\
fj.^
p = P,
'
(50)
Sm.^^
M^ dm ^,
/.I2
Mn^f^n^ MSni
and that
0,
(51)
Jje
for
TI))j\PI>v
J/,
Dm^  M^Dn,^
...
 M,,Drn^^
(52)
tions
each of the new parts as previously defined. If to these condiwe add equations (43), we may treat 1\ P, Jf^, J/g? ^n
simply as unknown quantities to be eliminated. In regard to conditions (51), it will be observed that
stance,
'S'j,
if
a sub
is
distinguished
negative, and
by we
a single ac<'ent,
shall
6m ^' may
^f^
;
be either positive or S^
is
have
/<i'
but
if
only a possible
component of that part, 6in^' will be incapable of a negative value, and we will have /^/^ J/,. The formulae (50), (51), and (43) express the same particular conditions of equilibrium which we have before obtained by a less genThis formula must hold It remains to discuss (52). eral process. in its varied state which in the system mass infinitesimal any of true any of the surrounding with homogeneous approximately is not B?n denoting Bm^, Bm Be, Bv, expressions />//, ^, the masses, mass, and the infinitesimal this volume of and entropy, the energy, as comregard which we *S' substances A'j, S^, the of quantities
.
posing
it,
(not
necessarily as
If there
is
which
this
as composed of these substances, we may choose whichever is most convenient. Indeed it follows directly from the relations existing
and
in
J.
W. Gihhs
129
any
case.
.
Now,
.
if
7>y,
Dm^.,
.
Dm.^,
for
Dnin are proportional to the A^alues of f, //, t;, mj, y/^^, any large homogeneous mass of similar composition, and of
.
. .
the same
this, that
f
is
equivalent to
_ T)i^Pv . .
J/,
J/2
///^
J/,
'''n
(53)
for
substances 8^,82 'S'. But the validity of this last transformation cannot be admitted
It
is
components of a very small mass surrounded by substances of different composition and state is the same as if the mass in quesWe started, tion formed a ])ait of a large homogeneous body. neglect the part of the that might the assumption indeed, with we
depending upon the surfaces separating heterogeneous Now, in many cases, and for many purposes, as, in general, masses. when the masses are large, such an assumption is quite legitimate,
energy,
etc.,
but
in
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 We shall see hereafter what large in proportion to the masses.
modifications are necessary in our formulge in order to include the
which are due to the surfaces, but this will be on the assumption, which is usual in the theory of capillarity,
parts of the energy,
etc.,
is
large in proportion to
is
neous
in
all
separates.
nature)
much
smaller than
if
when applied
dimensions
is
in
even of (52) as the necessary and sufiicient condition of equilibrium regard to the formation of masses not apprpximately homogeneoiis
with those previously existing, when the conditions of equilibrium
between the
it is
shown that
in establishing
17
October, 1ST5.
130
J.
W.
iJribhs
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
Dm^,
Dnio^
I>m that
this shall
be evidently the
have not been perfectl^^ 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
ex])ressions
is
Even
if
the
surface
energy
to
action of
tlie
two masses.
We
Now
^"^n
'^^'^
^^^^
defined that
none of
tlie
new
parts, shall
be violated.
These
that
new
entropy, volume,
of the system in its varied state are correctly of the energies, entropies, volumes, etc., of
represented
by tbe sums
the vai'ious parts (original and new), so far at least as any of these
quantities are determined or affected
parts.
We
will
suppose De,
TJi],
Dv,
Dm Dm^
^,
Dm,, to be
This
may
be
done
in various ways.
We may
we may supi)Ose this determined in any suitThus we may suppose the total enei'gy in and
about any new part to be so distributed that equation (12) as applied by the formation of the
new
parts.
Or,
it
imaginary surface which divides any new part fiom the original is so placed as to include all the matter which is affected by the
vicinity of the
new
we
regard as original may be left homogeneous in the strictest sense, including uniform densities of energy and entropy, up to the very
J.
W. Gihhs
surface.
JEquiUhriuni of Hetercxje.neoxx
Siihsfaiices.
13]
The lioniogeneity of the new parts is of no conwe have made no assumption in that respect. It may be doubtful whether we can consider the new parts, as thus bonnded,
bounding
sequence, as
to be infinitely small even in their earliest stages of development.
if
But
otdy
way
in
which
tliat in
e.,
which
it
(12)
would not
apply.
But
if
we
Hence,
finite
varied.
For the
dif
may
be considered as
made up of two
are for a constant nature and state of the mass, and the second
We may
new
parts to be
bounded
results.
as
The condition
(52)
either
of these
ways
(or
in
others which will suggest themselves to the reader) will have a perfectly definite meaning,
and
and
suffi
new
when
and
may
(50),
and
(43)
it is
always
To
piove this,
satis
fied,
only necessary to show that when (50), (51), and (43) are and (52) is not, (53) will also not be satisfied.
will first observe that
We
T}/
 Po f M^
m^
+ 31^ m^
.
+ Mm
(54)
denotes the work obtainable by the formation (by a reversible prom are the energy, cess) of a body of which f, //, v, m^, vy/g,
.
.
of the
components, within a
medium having the pressure P, the temperature 7\ and tiie potentials (The medium is supposed so large that its propM. ilfj, M2, erties 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
. .
of
tlie
if,
after the
1:52
J.
medium and
the
body, their joint volumes and joint quantities of matter, were the
same
body.
medium
This consideration
may
,
etc. this
when
f, ;/, //ij,
etc. are
P,
Jif^, etc.
do not represent the values of the temperature, pressure, and potenof any real substance.
actual components
(If
the substances
tS'^,
a>'.,,
S are
of a
which the equilibrium is discussed, that part will afibrd an example body having the temperature, pressure, and potentials of the
supposed.)
integrating equation (12) on the supposition that the
medium
Now by
the equation
we
obtain
t7/
+//n"?r.
(55)
which
for
will
Therefore
by
(50)
and
(51),
f
7'//
+ Pw J/,
is
/^
J/2?2
Mn>^=zO.
all
(56)
possible
new
which
the condition
expression
e
is
...
Mm
(57)
iV^,
be negative, and
decrease
if
the
number of
JV
is
will be
it
infinite.
Now we
need not
inquire wliether the least value of (57) (for constant values of T, P, M) would be obtained by excluding entirely the J/j, il/2,
. .
.
mass
iV^
and filling the whole space considered with masses or whether a certain mixture would give a smaller value,
like 0,
like
it
is
is
certain that the least possible value of (57) per unit of volume, and
by
homogeneity.
If the
new
satisfied occurs between two different original jjarts 0' and O", the may consider the ai'gument need not be essentially varied.
We
J.
W.
(rihhs
133
rated by a lamina N.
value of (57) lor a body consisting of masses like O' and 0" sepaThis value may be decreased by increasing
within a given volume
a convoluted form
by giving
it
and
it
will
be evident, as before,
homogeneous mass,
be negative.
And
posin
volume is the least possible for the same matter with the same entropy and volume, hence, if confined in a nonconducting
unit of
vessel,
it
will
be
in a state
Therefore
is
when
(50), (51),
and
not sat
isfied in
regard to
all
possible
new
be some homoaS'j,
iS^,
Therefore,
if
(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
is
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
all
large masses
this is
very
etc.,
Such an equilibrium
is
By
this
an
sufficient to
initial state,
perhaps a circumstance which entirely escapes our powers of percej)The presence of a small portion of tion, will be sufficient to do so.
the substance for which the condition (53) does not hold true,
cient to produce this result,
is suffi
when
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
(50)
little
be observed, that from (56) and (53) we can at once obtain and (51), viz., by applying (53) to bodies diftering infinitely from the various homogene<ms tarts of the given mass. There]
134
./
TK Gibbs
homogeneous parts bodies which can be any of the given mass) and (53) are always sufficient for equiwith formed of the given matter) (43) shall be equilibrium which for an librium, and always necessary
fore, the
condition (56)
practically stable.
And,
if
we
choose,
in regard to equations
(43).
For,
it
if
with
(38), it is
is
always immaterial,
consider
it
applying
the tests (56) and (53) to any body, how we Hence, in applying these tests, we may consider posed.
to be
all
com
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 Such these will vanish, and we need not regard the equations (43).
of the constants Jij, M.^
ponents,
.
.
M
and
compo
may
be regarded,
like
T anc\
(53).
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
m relate) that it the component substances to which m^, m^, shall be possible to give such values to the constants T, F, M^, M^.,
. . .
M in the expression {b1) 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
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
even when bodies can exist which are compounded in proportions infinitesimally varied from those of the solids considered.
e.
(Those solids which are capable of absorbing fluids form of course an It is true exception, so far as their fluid components are concerned.) 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 homogeneous 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
./
W. Gihbs
135
ponents of the
all
fluid, and the condition (53) is satisfied in regard to bodies which can be formed out of the actual components of the
fluid,
is
practically
which would
if it
were
fluid.
This follows directly from the principles stated on the })recedinoFor in this case the value of (57) will be zero as determined pages.
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
sufticient for equilibrium
masses.
a
is
its
possible
;
S,, be the actual components of the solid, and A',,, components (w^hich occur as actual components
S^
in the
fluid)
then, considering
solid as variable,
we
shall
have for
dv'
this
body by equation
, .
.
(12)
cW =
t ill]'
\ //'
dm J
dm,,'
+
By
this
f.1,,'
dm.,:.
(58)
//,/
//^.'
But the
dm^.',
considered as independent,
dently express variations which are not possible in the sense required in the criterion of equilibrium. might, however, introduce them
We
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 S^, of which the nature is represented by the solid itself.
We
may
then write
de'
=t' dt/
tij
d}uj.
(59)
In regai'd to the relation of the potential /// to the potentials occurring in equation (58) it will be observed, that as we have by integration of (58)
and
^'
(59)
i' '/'
 p'
e'
"'
+ /'/ ni,!
//
+
mj
//,/
//,; 1)1,;,
(60)
and
therefore
//^'
= mj =
t'
 p'
v>
+
.
//,'
(61)
(62)
.
fij
mj
.
m,'.
S,,
Now,
if
S^
and
S^.
the actual
components
iS,
we may
136
J W.
Glbbs
6e" =z
\
t" (h/"
li,,"
p"
.
+,/'" (^nta'
ji,:'
\l'J' ^^",i"
.
din,,"
^
Sm^:'\i.i,'' 6)11,"
l^i"
(hv'\
((53)
and
a8
by supposition
mj 2r =
m,,' '
ill,'
(64)
equations (43), (50), and (51) will give in this case on elimination of the constants T, P, etc.,
t'
t",
p
. .
=p\
.
(65)
//".
and
m;
i.>;
u,,; }i:'
+*;
(66)
may
and the
fluid.
The
last con
may
\iii,l
f.1,1
:=zm^
jinj
p{J'.
(67)
But
of S
6
.
if
.
all
S,
*S',,,
aS'x.,
S/
jS,
we may
///'
such bodies
t"
)/
f
p"
11
//" nt
.
...
. .
)ij'
m^
0.
(68)
it is
to be observed that
by
is
Now, by
is
(60),
and
member
state.
of this condition
zero
given
As
we
shall
have
(It
t"
f.i,i'
diitj
f.1,'/
dm,j
or,
/<//'
dm,' ...
///' diiti!
0,
(69)
by equations
(58)
and
(65),
{lij
Mc")
dnij
dm,'
{ {iij
;j,'')
d)iij
+
/jj
(/'///'/,")
(/<,'//,")
dm,'^
0.
(70)
/u,;',
/Y,;
=;/,;',
M,.'= Hi!\
Mt,'^
which with (65) are evidently the same conditions have obtained if we had neglected the fact of the solidity of one of
the masses.
J.
W. Gibbs
Equilibrium
of Heterogeneous Substances.
137
have su2)posed the solid to be homogeneous. But it is evident that in any case the above conditions must hold for every separate Hence, the temperature and point where the solid meets the fluid. 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
We
by the nature and number the independent variations Hence, if we reject as of which its nature and state are capable. improbable the supposition that the nature or state of a body can vary without affecting the value of any of these quantities, we may
the
fluid.
Now,
and exceed
in
fluid
which con
of the solid.
may
number of different
As
we have made
use, are
conditions of
equilibrium
But
number
the number of equations Yet the problem of equilibrium which has of condition is increased. sufficiently indicate method the to be pursued in all been treated will cases and the general nature of the results. It will be observed that the position of the various homogeneous
ished, in a case otherwise the same, as
is
otherwise immaterial,
may
is
deter
Thus, when
a vari
system
in
by
parts of
this sub
which
stance will be invariable for each of the parts of the system which are
arise
The
solid
III.
18
Novejiber, 1875.
138
tT.
Suhstcmces.
lem which we are next to consider there are equations of condition due to a cause of a different nature.
Effect
each of which
is
homogeneous and
fluid,
by
and
is
per
meable to some of the components and impermeable to others, we shall have the equations of condition
6v'=0,
and
for the
6v"=Qi,
(73)
67)1^=0,
dmj'=0,
6mi;=0,
6m,''=0,
etc.,
(74)
Sm/ +
With
rium
drn,''=. 0,
doi/ f 6m/'
0,
etc.
(75)
these equations of condition, the general condition of equilib(see (15)) will give the following particular conditions:
t'
t",
(76)
if
and
for the
actual com
=11,!',
///=//;",
p'
etc.,
(77)
biit
not
/.i,!=/.i",
nor
/,<j'
= p", =
//,,",
etc.
the diaphragm
ject to
may be expressed by equations linear between diti^\ will be which equations of condition, deduction of the the particular conknown 6m.,', etc., and if these be difficulties. no We will however ditions of equilibrium will present (being etc. actual components observe that if the components S^, /S2,
certain conditions, these conditions
on each side) can pass the diaphragm simultaneously in the proportions a 25 ^^^ (^vithout other resistances than such as vanish with
,
the velocity of the current), values proportional to j, a^, etc. are possible for 6i/i^', 6m J, etc. in the general condition of equilibrium,
6m, "
6m o",
we
shall
etc. having the same values taken negatively, so that have for one particular condition of equilibrium
aj yUj'+ 2
/'2'
tc.
= !
/f
,"
+ a2
//2"+
etc.
(78)
as
many independent
J.
TT".
Gibhs
139
as
t.liere
These conditions of equilibrium do not of course depend in any the supposition that the volume of each fluid mass is kept In constant, if the diaphragm is in any case supposed immovable. fact, we may easily obtain the same conditions of equilibrium, if we
way upon
the variation of the energy of the sources of these forces must appear
which will be
(U"
I"
(5v'
P" dv" ^
0,
(79)
(Compare From this condition we may evidently derive the same (14).) internal conditions of equilibrium as before, and in addition the
external conditions
P' and P" denoting the external forces per unit of area.
p'
= r,
it
p"
is
= F".
i.
(80)
permeabilit}'^ of
e.,
perfect,
and
its
impermeability absolute,
of the
that
it
components of the
fluids in
and
all.
How
is
of course to
be determined by experiment.
If the
diaphragm
is
permeable to
restriction, the
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?i + l independent variations in nature and state. Hence, if the fluid on one side of the diaphragm remains without change, that on the other side
cannot
sure
(in
will
may
be
a manyvalued function (or any one of several functions) of these But when the pressures are difierent on the two sides, variables.
the fluid which has the less pressure wdll be practicalhj unstable., in the sense in which the term has been used on page 133. For
f"
//"/;/"
0,
(81)
Therefore,
if
p'
<p"
while
t^
^^t".,
;(j'=;/i",
etc.,
140
J.
W. Gihbs
e"
t'
ij" \2)'
).i^'
m^"
j.io' n't'2"
/'n'
>'n"<0.
(82)
tlie fluid
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
of the diaphragm, the following relation will hold true in
fluids to
Then, as the
d?/',
heat received
by
the
and
as
Ttt"
^t'Di/
t"r)>/'
2)'vv' p"Tni",
(83)
by
(12),
//,'
Dm/ \(//,"
Ml" ^h"
+ /^2'
i^'^'s'
+ /^2" D^'s" +
i>"'2"+
etc.
^ 0,
(84)
(85)
or
///) i>m,"=
i/io"
 Ms)
etc.
to.
It is
which we have been depend upon the equations which express the relations between the energy, entropy, volume, and the quantities of the various components, for homogeneous combinations
Tlie solution of the problems of equilibrium
made
to
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
for
each
energy and
its
entropy are
both zero. The values of the energy and the entropy of any compound bodv 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 and its are zero into combination and to the state in question
;
entropy
is
for
any
reversible process
J.
141
[dQ denoting an element of the treated, and t the tempeiature thus heat communicated to the matter both of the energy determination In the of the matter receiving il).
by which
effected
and of the entropy, it is understood that at the close of the process, all bodies which have been used, other than those to which the determinations relate, have been restored to their original state, with the exception of the sources of the work and heat expended, which must
if
homoge
neous mass containing n m will and not its nature or state, the quantities f, ?/, v, m,, mg, learn if we sufficient is it therefore all vary in the same proportion quanof these one from experiment the relation between all but any
.
tities for a
Or,
we may
f, ij,
consider
that
we have to learn from experiment the quantities between the 7i 4 2 ratios of the n {
'i
. .
.
relation
subsisting
v,
m^,
^,
rn^,
,
m^.
that
,
To
is,
fix
our ideas
we may
, ,
etc.,
and
which
may
is
may
be more convenient to
it is
ni in m
,
,
In any case,
variables, of
is
Now
if f is
known
function of
//,
w,
m^, m^,
?,
as
by equa
tion (12)
dE=Lt
di]
pdv
^^ dni^
/1 2
dni2
/<dni,
(86)
t, p, pii, 1^21 /^'n ^'"^ 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 2n + 5 variables, e, ;/, v
w?j,
mg,
m, t,p,
yUj,
Uo,
are
//.
These are
all
of these variables,
evidently independent.
Now
its
upon
compound
considered,
we
may
say
in
general,
all
thermal,
which
all
these relations
may
142
J.
W.
G'lbhs
Equillhrmm of Heterogeneous
Substances.
fundamental equation for the substance in 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 / is to isotropic stresses an equation between , ;/, v, m^,m,
be deduced
question.
will call a
we
We shall
hereafter consider a
a fundamental equation.
this
which possess
same property.*
Let
t=:et
;/,
(87)
we
obtain
+/'f.c?>yi.
=
//'
//dt
pdv +
/'n ill
//,
dm^

^2
t,
f^'^2
(88)
then,
1/,
is
known
as a function of
v,
^^ ni.^,
m,
If
find
p, Ml, /'},
//'
we can we then
substitute for
in
we
shall
have again n
as before.
X=e+pv,
dx
If,
(89)
tdif
+
. .
dp
+
in
/<!
(7m
/'g ^^'"2
+
.
/' ^^"^n
(90)
then,
t,
X be known
/.i^,
.
as a function of
//
?/,
p,
m^,
tn^,
?;?,
find
V, /^j,
we can By elimi
nating Xi we may obtain again n + 3 independent relations between the same 2n + 5 variables as at first.
Let
K
=s/^i
t,j
+pv,
f
(91)
then,
by
(86)
i]dt
\
d'Q=~If,
dp
{
dm^
ji2dm
#,
f
/'f?wv
.
(92)
then,
'C,
is
known
as a function of
p.,
m^,
m.^,
we can
how
* M. Massieu (Comptes Rendus, T. Ixix, 1869, p. 858 and p. 1057) has shown all the properties of a fluid " which are considered in thermodynamics" may be
considered.
viz.,
deduced from a single function, which he calls a characteristic function of the fluid In the papers cited, he introduces two different functions of this kind
a function of the temperature and volume, which he denotes by
ip,
the value of
e
7
tr/
which
in our notation
would be
or
tp
;
rp',
y
t
jj'y
or 7.
of the
fluid,
which
is
yWn ^n,
144
J. W^.
'
the subscript numerals refer, (but not excluding the case in which
1 and the composition of the body is invariable,) there is a relabetween 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 ielations subsisting for such a mass between the quantities 6, iii, t, jy, ji^, pi.^, //, y, ni^^ m.^, j,
//
tion
//,
i:,
ii.
It
will
be observed that,
theie is
besides
the
equations which
define
^',
j,
and
c,
one
which subsists
between these
equation.
q^^antities
might of course be added which possess mentioned on account of the important properties of the quantities i/\ j, and
Other
sets of quantities
the
same property.
The
'Q,
(88),
(90),
convenient
;,,=(*)
etc.,
=(m
letters
=im
m
=(/L)
(104)
all
the
m^, r/ig, 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 quantity
equation
//'
the quantities
ip,
x,
'i
by
the
//'
~
m,, m2,
ttj.
(105)
between
e, ?7, ,
.
m
m.
V,
m,,
m.2,
As. by (86),
^= il)
the second equation
may
first.
But the
first
equation
(^)
ldv\
V,
TO,,
m,,
TO
is
[del vm
'
"^M 2!
^n//
which
is
in
variables.
J.
W. Gibbs
Equilibrium
of Heterogeneous Substances.
145
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 (106) f,l"=ee''t(v'~>j"). If we suppose the system brought from the first to the second of
which
is
the
system, then
and Hence
and
for an
t"W Q, = Q. t{7i" ~
]/)
{101)
(108)
(109)
in
ff' = W',
infinitely small
reversible
change
the
state of the
we may
write
(110)
dip = dW.
Therefore,
//'
is
temperature, just as
//'
is
That
is, if
we
consider
and the
//'
is
required
by the system
that
if
temperature.
From
and
this
we may conclude
equilibrium
may
be expressed by
(Ill)
(2) in
W).^o.*
* This general condition of equilibrium might be used instead of
after with evident
such prob
lems of equiUbrium as we have considered and others which we shall consider hereadvantage in respect to
<
tlie
in (111) applies to
we have
to consider.
in this
the particular
conditions of equilibrium from one general condition, and of having the quantities
mentioned
defined
;
and because
each
we should adopt
which would be
and
remaining conditions.
For example,
in the
problem
we would
III.
would be wanting.
19
January, 1876.
146
J.
TK Gibhs
it is
When
and
it
'/;"
rehite
by a
will
be observed that
not necessary
system
TFand
relate,
provided that the only source of heat or cold used has the
as the
same temperature
external bodies
system
in its initial or
in
final state.
Any
aifect
may be
may
be restored to the
it
maybe
interesting to
(2)
tions (111)
in the
and
given state
is
uniform throughout.
in the state of such a
If there are
any variations
<
its
and
6t; :=. 0.
If the
not uniform,
its
energy
will
pass from
warmer
to
And
For
S<Q
Hence, as we
and
(SjjX).
may
ing the system, there must be a state of uniform temperature for which (regarded as a variation of the original state)
6e<0
From
this
and
djj
0.
we may conclude
we
we
t6t/=z6f]t/6t.
(112)
Now
by heating
 t6?j=0
and therefore
rh/
f
?/ f)7
0,
(113)
J.
W. Gibhs
147
is suffi
equivalent to
(114)
tdi]^0.
equivalent to
is
6il^{if6t^0
(115)
we have
in
which
composed
these
when
may be
conveniently expressed
by means
of the func
C, which has been defined for a homogeneous mass on page 142, and which we will here define for any mass of uniform temperature and pressure by the same equation
= e tt]\pv.
(internal) equilibrium is
(Ii6)
m,p^^That
this condition is equivalent to (2) will easily ap[)ear
(iiv)
from con
Hence,
it is
quantities of the
equal.
Or,
necessary
first
for
mass
Thus,
sum
of the values of
is in
composed of <i i)arts of water and b contact with vapor of water and crystals of
C
true in
more complicated
cases.
The reader
deduce these
given on
page
128.
In like
combination of masses
using
s
definition of x to any mass or which the pressure is everywhere the same, for the energy and v for the volume of the whole and setting
in
as before
X=t\pv.
(118)
48
J.
W.
Gihhi^
If
we
denote by
not varied,
and
and
final states of
the system
by accents
(iif)
we have
x"
x'
= ^"
f'
+i>
('""
"')
= Q
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
by
the
system.
In
all
allowed
I'emains michanged.
POTENTIALS.
In the definition of the potentials
/z^,
/y,,
etc.,
the energy of a
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
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
mass, until
we have
fixed the
manner
in
if
sidered as composed.
For example,
by
tion,
we may
m^ weightunits
of the
hydrate and
It will be observed that the values of m., and salt and m of water. m, are not the same, nor those of m. and ?,, and hence it might seem that the potential for water in the given liquid considered as
composed
of the hydrate
and water,
ds
I
\
viz.,
Xdinjylr/,
V,
ms
would be
sidered as
different
from the potential for water in the same liquid concomposed of anhydrous salt and water, viz.,
dmjr),
V,
m.
./.
W. Gihbs
of the
149
The value
m^is
two expressions
m,^.,
for,
although
not equal to
we may
c?m,
in the
two
when
the
quantity dm^y or
dni,
of water
added without altering the entropy Precisely the same considerations will
is
we may
sidered.
combination of elements
neous body.)
(For the purposes of this definition, any chemical element or in given proportions may be considered a
In the above definition we may evidently substitute for entropy, volume, and energy, respectively, either temperature, volume, and the function or entropy, pressure, and the function j or tempera?/ ;
;
ture, 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.
'Q.
same homoaS^.,
geneous mass the same equations will subsist as between the units
That
is, if
the substances,
aS', aS',
etc.,
/S'
etc.,
/^
+ etc. =
+ A ,
 etc.,
20)
a, 6, etc.,
and
etc.
a,
/J,
etc., h, A, etc,
denoting the units of the several substances, denoting numbeis, then if /<, //, etc., /z^, //,,
mass,
a /<
To show
this,
4
fJ
//,,
+ etc. =
/ii
//,
+ etc.
(121)
Then, the
we will suppose the mass considered to be very large. number 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
first
150
J.
W. Gihbs
matter represented by the second member of (120), the entropy and A^olume of the mass remaining in each case unchanged. Therefore, as
the two
quantity, the
But
it
is
intended to
denote equivalence of the substances represented in the mass conin other words, it is supsidered, and not merely chemical identity posed that there are no passive resistances to change in the mass
;
member
For
by the
other.
example,
in respect to a
and oxygen
(at
ordinary temperatures),
we may
not write
but water
is
and no neces
sary relation will subsist between the potential for water and the
potentials for
The reader
(43)
by equations
(which are essentially relations between the potentials for actual components in diffeient parts of a mass in a state of equilibrium) are simply those which by (121) would necessary sub
and
(51)
sist
as variable
relate.
between the same potentials in any homogeneous mass containing components all the substances to which the potentials
In the case of a body of invariable composition, the potential for is equal to the value of C for one unit of the
'
r=j.im
(122)
Therefore, when n =. 1, the funto which (96) reduces in this case. quantities in the set (102) (see page damental equation between the
143) 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.
Also
in the case of a
body of
variable composition,
when
all
the
We
J.
W. Gibhs
151
for one unit of a body may always be Hence the relations between the values of for contiguous masses given on page 14Y 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 All other bodies used in the ])rocess must by its close be part.
considered as a potential.
t,
state, except those used to supply the work, which must be used only as the source of the work. For, in
a reversible process,
altered, the entropy
when
the entropies
not be altered.
But the
zero
substance.
of the energy of the mass and substance taken together, and therefore
equal, as the original energy of the substance
zero, to the
increment
by
The
homogeneous mass
is
equal
by
a reversible
which 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
process from a state
in'
ij:
(109) to the
The
very
how
the value of
in the
the potential
affected
definition of the
stance.
in
energy and the entropy of each elementary subFor we may imagine the substance brought from the state
//'
which
=:
is
the
same
152
J.
W. Gibbs
to
Equilibrium
mass,
first
any
work expended
'/',
is
Let this be
denoted by
and
in
let
/<
in question,
and
then
W the
(123)
work expended
mass
as aforesaid
[
W.
Now
6=0
and
//
zz:
is
arbitrary,
we may
the substance in
possible states
in
all
The value
of
t
'/,
or e
f //,
for
by any constant C, and the by any constant IT. any state would then be increased by
possible states
state.
C^
to
//''
JC,
Applying
this
is
in (123)
last
term
in this
equation
independent of the values of these constants, we see that the potential would be increased by the same quantity C ( K, t being the temperature of the mass in which the potential
is
to be determined.
modynamic
form.
term which shall refer solely to the composition and therstate of any such body without regard to its quantity or
We
may
call
dif
phase.
only in quantity and form as different Phases which can exist together, the dividing surfaces being
plane, in an equilibrium
ances to change,
If a
we
homogeneous body has n independently variable components, body is evidently capable of n. } 1 independent variA system of r coexistent phases, each of which has the same ations. r varian independently variable components is capable of n { 2 For the temperature, the pressure, and the potentions of phase. tials for the actual components have the same values in the different phases, and the variations of these quantities are by (97) subject to Therefore, the numas many conditions as there are different phases.
the phase of the
ber of independent variations in the values of these quantities, i. e., the number of independent variations of phase of the system, will be
n+2
r.
./.
W. GibbsEquilihrhtm of Heterogeneous
r bodies considered
if
Substances.
153
Or,
when the
variable components,
we
still
number
is
capable will
be n\2 r.
In this case,
it
will
be necessary to
substances.
n component
Let
We
shall
have by
(97), as
pressure,
and
(51)
and of these n + h potentials, and we shall also have by (43) h relations between these potentials, of the same form as the
which subsist between the units of the
if
relations
different
component
substances.
Hence,
r z= w
2,
no variation
in
istent) is possible.
71
It
example of n =z 1 and r z=. 3 is seen in the coexistent solid, 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
liquid,
+ 2. An
but
it is
An example
of
7i
=2
and r:=4
is
seen in a
two
Concerning n
\ I
Coexistent Phases.
now seek the differential equation which expresses the between the variations of the temperature and the pressure in a system of w f 1 coexistent phases ( denoting, as before, the number of independently variable components in the system taken as
will
We
relation
a whole).
In this case
we have
//,
>i
the quantities
accents.
v,
mj, m^,
etc.
But
is
and^
will each
the same
true of
different equations.
If the total
number
of these potentials
is
+ A,
may
the h independent relations between the units of the component substances to which the potentials relate,
by means
of
which we
20
January, 1876.
154
J.
W. Gihhs
dp=z
+ mj
dj.!^,
m,'
dfij,
+
.
etc.,
(124)
let it
become
.
\A,!df.i.
(125)
be observed that
//,
which may or may not AS'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 substances, (compare equations (38), (43), and (51),) if we denote these units by , j, etc., i, 3, etc., we must also have
the mass considered for a substance
y8j,
^?\'a
+ ''6'A+etc. = ^/ 1 + ^12' 2
member
+^^n'. (126)
But the
first
the matter in the body to which equations (124) and (125) relate.
the same must be true of the second member,
As
same
we may regard
this
body
as
quantity
AJ
We
m^\
A ^\ ^2?
rnj
djJ^.
^^' ^"
which
\i'
will then
rf
become
dp=L
dt
^^
m^ d}.i^
{ rn^
dji^,
{
(12V)
to
as are the
(97)
and
to a
(124) relate.
The
rest of the
71
equations
may be reduced
^m^'dpt^,
dp
etc.
= if dt
7n^"
df.1^
^m.^'dji^
(128)
By elimination
V
of
<:?yu,, df.i^t
dj.4
J.
W. Gibhs
11=. 1,
155
When
or, if
(/' v'
dp
1,
{m"
if
(130)
we make
ni'
=.
formula
(131)
^
'
dt
in
v'v"
t{v"
v'Y
which
is less
When
7i>
1, if
the quantities of
all
Sg,
S^
are proportional in
be
sufficient
In fact,
the condition of the coexistence of the two phases together with the
condition of the equality of the n
ratios of
w/,
mg',
?'
with the n
ji>
wi" is sufficient to
is
determine
as a function of
if
known
for each of
the phases.
in the
The
may
be expressed
one
to
if
of the
form of (130), m' and m" denoting either the quantities of any components or the total qiiantities of matter in the bodies
relate.
which they
in this case,
unity.
But
in that the
the heat
in
letters in the
is
is
essentially
when
tlie
it
is
a crystalline body,
(131) relate will
matter to which
letters in
When n =
ature
is
hold true in
two coexistent phases are capable, when the temperBut as (130) will this case when m^' m^ m/' ni^'^ it follows that for
2,
:
is
in general a
is
maximum
identical.
is in
or a min
imum when
two phases
In like
general a
maximum
of the
two phases is identical. Hence, the series of simultaneous values of t and p for which the composition of two coexistent phases
156
is
TF.
Gibhs
Equilibrium of
Ffeterogeiieoiis Substa7ices.
and
2^ foi"
which
no coexistent phases are possible from those for which there are two
This may be applied to a liquid having pair of coexistent phases. two independently variable components in connection with the vapor which it yields, or in connection with any solid which may be formed
in
it.
When
V
z=. 3,
we have
we may
V
V
m m
m,
rf
m^
tn^"
m^
tn^'
df
dp=.\?f
\
m,"
dM^. (132)
Now
when
two.
when the above condition in regard to the composition of the coexistent phases is satisfied. The series of simultaneous values
which the condition is satisfied separates those simultaneous values of t and /> for which three coexistent phases are not possible, from those for which there are two triads of coexistent These propositions may be extended to higher values of ?i, phases.
of
t
and
2^ foi"
and
illustrated
71
by the
solutions of
INTERNAL
STABILITY OF
AS INDICATED BY
We
will
now
a rigid
all
envelop which
is
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 /She every respect throughout its whole extent. Let S^, S.j, we may then consider every the idtimute components of the fluid body which can be formed out of the fluid to be composed of /S'j, /Sg, m denote Let m^, m^, that in only one way. ;S', and the quantities of these substances in any such body, and let f, //, v,
. .
.
denote
for
its
compounds
all
aS',
if
us
oeneous bodies.
J.
Substances.
157
is
.
possible to assign
Tt]\
Pv ~ J/, mj  M2 m^
fluid,
3fm
(133)
and shall be positive for every other shall be zero for the given 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
stable.
aS\,
/S'g,
. . .
/S),
For,
in
homogeneous, or
is
not
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 (That this conclusion cannot be condition of the mass is positive. 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 131133.) 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 con(See page 110.) dition is therefore stable.
Again,
if it is
(133) that the value of the expression shall be zero for the given
fluid mass,
and
shall not
page
110.)
It will
be stable unless
in the given
volume and with the given entropy to consist of homofor all of which the value of the expression (133) is zero, but M^hich 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 133, 134.) In this case, if we disregeneous parts
gard the quantities connected with the surfaces which divide the
*
vacuum
158
J.
W. Gibhs
Equ'dihfium of Heterdgeneous
we must regard
But
in
Siibstances.
homogeneous
parts,
neutral equilibrium.
which we may evidently consider to be all diiFerent phases, the fol(The accents distinguish the satisfied. letters referring to the different parts, and the unaccented letters
lowing conditions must be
refer to the
whole mass.)
rf
+ if + etc. =
+
v"
\ etc.
/^,
v'
1
I
V,
?Mj'
=/>!',,
)^
(134)
etc.
Now
fluid
the values of
//,
v,
m^, m2,
etc.
are determined
of
by the whole
etc.,
mass
^,
in its
,,
j.
jj.
etc.
>,
etc., etc.,
by
parts.
They form,
between
v',
in fact, tlie
whole
set of
latter is one.
Flence,
v" , etc.
we may regard
(The values of
linear equations
v",
etc. are also subject to the condition that none of them can be
negative.)
Now
and
it is
the
phases,
it
than n
2.
We
is
is
mass
will
be
in neutral
if
of the substances,
which the value of (133) is zero (when the constants are so determined 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.
xS'g,
. . .
When
S are
all
independently vari
evident from (86) that the conditions 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
able components of the given mass,
it is
only be
fulfilled
when
M^,
are equal
to the temperature, the pressure, and the several potentials in the given
J.
Substances.
159
mass.
If
we
will necessarily
give these values to the constants, the expression (133) have the value zero for the given mass and we sliall only
its
value
is
positive for
all
other phases.
1S2,
S are not
all
will
be necessary to give
but
it
and
must be equal to
its
will
be easy to obtain as
many
eqiia"
mass
as
it
When
fluid,
it is
(133) that the value of the expression shall be zero for the given
and either zero or positive for any phase of the same compowe have already seen (pages 129134) that if equilibrium subsists without passive resistances to change, it must be in virtue of properties which are peculiar to small masses surrounded by masses of different nature, and which are not indicated bj' fundamental
nents,
equations.
we
in
degree through
by
fundamental equations
sense.*
*
If
will
in this
we wish
to
know the
enclosed in the same envelop witli the given fluid another body (which cannot combine
with the
fluid) of
Ty, or
= ~ Fv.
or
T>)
Pv.
which
as the case
of course
may
be,
(Tand
P denoting
it is
must be those
and
page
When
fluid
and
positive
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.
fluid are of
Hence the
fluid is stable.
When
is
it
is
stants that the value of (133) shall be zero for the given fluid
fluid
of course unstable.
when
it is
possible to assign such values to the constants that the value of (133) shall be zero
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 possibUity of satisfying, for any other than
fluid,
first
we
60
.7.
W. Gihbs
and any
M whether the expression given values whatever of 31^, M2, (133) is capable of a negative value for any j^hase of the components
*S', and if not, whether it is capable of the value zero any other phase than that of which the stal)ility 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 mis capable of at least one state ot by any values of w^j, w^, not unstable equilibrium (which may or may not be a homogeneous It may easily be shown state) at this temperature anrl pressure. that for such a state the value of f T7}\ Pv must be as small as The same will therefore be for any other state of the same matter.
/Sj, JS^,
for
Therefore
if this
expression
is
capable of
any mass whatever, it will have a negative value And if this for that mass at the temperature T and pressure P. mass is not homogeneous, the value of (133) must be negative for at So also, if the expression (133) is least one of its homogeneous parts. any phase of the comj)onents, of negative value for capable a not value zero must have the temperature any phase for which it has the and the pressure P. may easily be shown that the same must be true in the limiting and Pz= 0. For negative values of P, (133) cases in which 7'= is always capable of negative vahies, 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
It
?
J/i m, J/2
. . .
^"'2
3/m.
(135)
We
(133),
M and v have any given finite P, 3/,, ll^, values, cannot have an infinite negative value as applied to any real body. Hence, in determining whether (133) is capable of a negative jS, and if not, value for any phase of the components >S',, S^^
when
T,
. . .
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 Any least value of which it is capable for a constant value of v. body giving this value must satisfy the condition that for constant
volume
de
Teh/
J/j
drn^
J/^
din.,
...
3fdm^
0,
(136)
stability of the fluid for constant temperature, or for constant pressure, or for both.
The number
the remaining equations, and then the equilibrium of the fluid will be neutral in
respect to one or
J. TT.
Gibbs
161
or, if
we
a
g for the quantities rehiting to tlie actual corai)onents the body, and subscript h k for those relating to the possible,
script
. .
.
t di]
yM
dm,,
...
+
Jfj
yM
dm,,
f
/</,
dm,,,
/^^.
dm,^
0.
That
is,
Tdi]
dm^
M2 dm^
...
 Mdm^
(137)
body must be equal to T, and the components must satisfy the same conditions as if it were in contact and in equilibrium with a body having potentials M. Therefore the same relations must subsist between Mj, M2, yu Jf as between the units of the corresponding //, and M^
the temperature of the
its
potentials of
substances, so that
m^.lA^.
. .
= m^
M^^
{
mM;
m^,
(138)
and as we have by
(93)
7]
E=.t
pv
\ /A
m ...}
yu,,
(139)
it
body
[Pp)v,
the value of
(140)
P
in
(141)
is
fluid of
which
all
the ultimate components are independently variable admit a very simIf the pressure
is
other phase of the same components which has the same temperature
components, the
is
if its
pressure
;
not as great
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 Avhich the tests
as that of
But
if
we should form
21
arbitrarily
any equation as
January, 1876.
a fundamental equation, and ask whether a fluid of which the properTrans. Conn. Acad., Vol.
III.
162
ties
J.
Wl Gibbs
were oiven by that equati<in would be stable, the tests of stabilitylast given would be insufficient, as some of our assumptions might
not be fultilled
by the equation.
all
test,
cases be sufficient.
Stability in respect to
may
take place
in
any mass, we
phases.
new
phase of a
fluid
may be
and unstable
In this case
it
may
be capable
unstable
mencement
of discontinuous changes.
in regard to continuous
changes
is
change.
We
will
now
may
also
be
called,
We may
from
use the
little
tlie
phase of which
in question.
In
tliis
case the
component substances
J/g?
to be considered will be limited to the independently variable com'^tc. must have the 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 infi
ponents of the
fluid,
il/'j,
become
but
if
be stable.
case, in
in
adjacent phases.
be
of stability,
This condition, which for brevity's sake we will may be written in the form
e"
condition
t'
if
jo'
v"
/</;,"...
/4'
m"
> 0,
(142)
in
in
which the quantities relating to the phase of which the stability is question are distinguished by single accents, and those relating to
J.
W. Gibbs
103
by double
This condition
is
by
(93) equiva
e"^t'if^p'v"~n,'m,"
//'m"
jji'
and to
f'4
'///
w'
{/<,
'm/
.
m'
> 0, > 0.
in the
(143)
^t'7f\p'v" fi.'m,"
~/^:m"
.
t"
yf
 p" v" +
A'
x"
m,"
+
. .
/."
mj'
(144)
The condition
(143)
may be
form
(1^5)
Ae.>tAn~iy^v +
if
{jjzlm,
we use
the character
to
ance with the usual convention in respect to differential equations with neglect of infinitesimals of higher orders than the
In fact,
first,
but
is
when
is
satisfied
must be possible
which
of
it
But
it
is
to be
remem
by a
(If
would evidently be zero.) We may free ourselves from this limitation by making v constant, which will cause the term p Jv to disappear. If we then divide by the constant v, the condition will become
member
of (145)
A>tA\i.i.J~^
in
+yuJ
(146)
which form
it
As
we may
d=itd^ 4 /.i,d^
we
see that the stability
4u^d^,
to
(147)
continuous changes
to the
second
and higher
of of the density of entropy and the densities of the several components, which would maJce the density of energy a minimum, if the necessary
conditions in regard to the first differential coefficients were fulfilled. When n rz 1, it may be more convenient to regard ui as constant
164
fZ
TK Gihhs
than
v.
in (145)
Regarding
of a phase
and higher
regarded as a function of
the energy a minimum,
if
were
fulfilled.
The formula
to
which
t',
/>',
relate.
tlie
But
it
is
sufficient condition of
matter, or of
of
all
any two
same
limits, or,
as the case
collective
may
be, in general.
therefore, of such
determinations of stability, we
may
form
(148)
or
1}
Jt{ V
Jp
m^
J/Y J
...
 m^ J// > 0,
.
Jp>ljt+'^J,i,
Comparing
bility in
(98),
4^^/V
(149)
we
see that
it is
given limits, that within those limits the same conditions should be
fulfilled in respect to
the pressure regarded as a function of the temperature and the several potentials,
if
the
differential coefficients
were
fulfilled.
By
may
be brought to
the form
^f
For the
and
true of any
t'
if
p'
m^'
+//';/'>
limits
0.
(150)
any given
it is
necessary
sufficient that
This evidently
requires that
when v'=
y", //</
/></',
m^
=z
?",
f f+{t" t'),/'>i);
and that when
t'
(151)
t"
f ~ p'
r'
\ fi
^'
^'
\
jjj
mj > 0.
(152)
in the
form
J.
W. Gihhs
165
(153)
+ vAt\^<0,
.
[/iil:\2)^'0
 X^Am^
// Z/>?i],
> 0, m
,
.
(154)
in
which are to be
.
m. standing for all the quantities regarded as constant, 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
by
the equations
t'"
t\
(155)
.
and
v"'
= v",
m,"'
= m,",

m"'
= m".
(156)
Now
by
(153),
'/'"'/"+(^"'O'/"<0;
and by
(154),
(157)
f"
J^ p' v'"
1^1
^'
m^'"
/V >/''"
\
//''
j^v'
i//,'/n/
^aJ tnj
>0.
(158)
t'" //"
p'
v'
//
'
m/
//' ///'
> 0,
(159)
which by (155) and (156) is equivalent to (150). Therefore, the conditions (153) and (154) in respect to the phases within any given
limits are necessary
and
phases
be observed that in (153) we have the condition of thermal stability of a body considered as unchangeable
within those limits.
It will
in composition
ical
and in volume, and in (154), the condition of mechanand chemical stability of the body considered as maintained at a Comparing equation (88), we see that the constant temperature.
condition (153) will be satisfied,
cific
if
^ <0,
i.
e.,
if/
or
^
1,
i.
(thespee.,
is
positive.
When
/^:=
when
is
(154) will
we regard
as constant,
by which the
{Af
+ p Av\,>().
if
(160)
^ >0, dv^
i.
e.,
if
L
dv
qy
d7)
v~
(the
elasticity for
constant temperature)
is
positive.
But
when
n> 1, (154)
may
V constant.
(142)
may
be brought to
166
J\
W. Gihhs
^"
Equilibrium of Heter
all
0(1 eneous
Substances.
j^t",fp"v"
t'
if
ix.'m,"
lA^m:
/'n'
l;'
+y
v"
+/<///... +
ra:
> 0.
(161)
it is
7/Jt
.
.
V /lp],,<0,
(162)
and
[JCyU,^mi
as
ywJm],,,>0,
(163)
may
easily be
The
first
body considered as unchangeable in compoand the second the conditions of chemical stability for a body considered as maintained at a constant temperature and pressure. If m^, n z=. 1, the second condition falls away, and as in this case C
ditions of stability for a
sition,
The foregoing
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) involve
in general several particular conditions of stability.
ofive our attention to the latter.
<^
We
will
now
(164)
Let
=:
t' 7}
+p
^^' m^
/V>^n,
the accented letters refeiring to one phase and the unaccented to It is by (142) the necessary and sufficient condition of the another.
stability of the first phase that, for constant values of the quantities
and of
is
v,
the value of
shall
first.
be a minimum
Differentiating
d^={t 
t')
ch]
{p p') dv +
(/ij
/f,')
dm^
(//
^')dm.
v,
(165)
. .
we regard
m^,
having the constant values indicated by accenting these letters, t shall be an incieasing function of ;/, when the variable phase differs But as the fixed phase may be any sufficiently little from the fixed.
as
stability,
for
This condition
may
be written
1^)
>0.
(166)
J.
W. Gibbs
167
Wlien
of
y,
this condition
,
.
satisfied, the
value of
(Z>,
for
?/',
will
And
therefore, in
we need only consider the j)hases for which t = t'. see again by (165) that the general condition requires that rn as having the constant values indicated if we reoard t, v, m^,
(f ,
We
by accenting these
when
from the
fixed.
l)ut
//
j
may be any
;;,
. .
.
must be an increasing function of m^ (within these That is, m. w, mo, constant values of
any
(pX \nm^!t,
V, m.2
>0.
will
. .
(167)
When
imum
and
yu,
have a min
value, for
v,
m^,
',
when
t'
A<j'; so that in
t' and /<, = yw/we need only consider the phases for which t particular conditions following the obtain also In this way we may
of stability
(P) \Zlm2ft,
\JmJt.
>0,
V,
(168)
m,,
m;5,
?n
>0.
V,
(169)
When
the n\
all
satisfied,
be a
minimum when
perature and the potentials of the variable phase are equal to those
of the fixed.
will
will
The
be entirely
identical.
satisfied,
be completely
the
when
satisfied.
which these particular conditions have been m^ we may interchange in them ?;, m^, in any way, provided that we also interchange in the same way
From
manner
in
derived,
it is
evident that
^,
yUj,
/J.
In this
way we may
in
?i
The quan
might be included
the
first
of these
lists,
and
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.
168
Tlieii
fZ.
W. Gihhs
tuted for the condition that the volume shall be constant in the state
minimum
To indicate more distinctly all these particular conditions at once, we observe that the condition (1^4), and thei'efore also the condition obtained by interchanging the single and double accents, must hold
true of any
stability.
(t"
two intinitesimally difiering phases within the Combining these two conditions we have
limits of
t') (;/"
//')
(/' i>')
v')
+ (/^i"
which
y"i') h'^x"
''H')
. . .
/^')
'm')>0,
(170)
may
^tJjj /ip^v
+ Jfx^/lm^
+z/yuz/m>0.
(iVl)
This must hold true of any two infinitesimally difiering phases within If, then, we give the value zero to one of the the limits of stability.
difierences in every
completely identical, the values of the two differences in the remaining term will have the same sign, except in the case of Jp and Jv,
which
will
have opposite
signs.
(If
two
J)
in
except p and
If
any term of (171) in an increasing function of the other, when we regard as v, of which the opposite is triie,
constant one of the quantities occurring in each of the other terms, but not such as to make the phases identical.
we
write
^?
for
/}
in (166)(169), stability.
aie
always
sufficient for
If
when
r^,
v,
m^,
are
When
,
.
dv =:
^
0,
we
^
shall
have
dt=z
dt
dy
df]
dt + dm dm
,
z
dt d)n + am
du.
d^x^
du
(172)
d^^=^dv\^^^drn,
d^
dfi
+^fm
d^
J.
W. Gibhs
169
Let us write S+i for the determinant of the order n d^8 drf
d^e
d.T]
d^e
d^E
'
dm
,
dy}
'
'
dm djj
d^e
d^E
d)n
dm
^
j
dm. dm.
(173)
d^E
di]
d'^E
dm
dm, j
dm
'
dm,'^
by
t'tc.
(86) the
for the
same
as the coeificients in
minors obtained by erasing Rn^t, column and row in the original determinant and in the minors
i?,
H^
for
the last
all
dfi.^,
f?/'_i,
and dv
Ii dpi,
= ^+i dni,
/^\
In like
=^K
(175)
manner we obtain
\dm_Jt,v,ii,,
etc.
f^n^Z^
(176)
by writing d
for /} in (166)(169)
are equivalent to this, that the determinant given above with the
it
as
last
remaining
this con
all
be positive.
Any
]^hase for
which
dition is satisfied will be stable, and no phase will be stable for which any of these quantities has a negative vahie. But the conditions (166)(169) will remain valid, if we interchange in any way
Tf,
W2j,
m, (with
corresponding interchange of
^,
/ij,
//).
in
in
which we erase successive columns with the corthe determinant is immaterial. Therefore none
by erasing
We will now
of
stability
(i. e.,
22
January, 1876.
170
tT.
Substances.
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
into
in the first
memis
(That
it
the
numerator and not the denominator in the differential coefficient which vanishes at the limit appears from the consideration that the
denominator
phase
is
is
in
is
capable of variation at
letters.)
all
by the subscript
ferential
The same
coefficients
. . .
m, and simultaneously interchanging t, /x^, m,, /u^ same way. But we may obtain a more definite result than this. to m_^ or /*_i, and to v, Let us give to ?/ or t, to m^ or /^j, Then the constant values indicated by these letters when accented.
/;,
.
way
in the
by
(165)
d^ =
{pt
 /tj)dm.
(177)
Now
"""(.Irj'c"""'')
(")
and
its
accented letters
Therefore,
and
as {vi
1 i
[<^l'A'r (4/7,
rn,
The
same order
different
mj)^.
Now
/;
this value of
will of course
be
(the
differential
coefficient
or
made
i/i^
or
pi^
constant, etc.
the value of 0, for any constant values of ?n and //_, have the values indicated when t,p,/iXi
. .
.
be the least
by accenting these
letters,
* 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 See pages 152156. already been considered.
J.
W. Gibbs
171
when we give
when we
regard to the
And
.
. .
in
if
all
these relations
we may
interchange in any
way
?/,
w,,
m,
we
/./.
It follows that,
for
diiferential coefficients
du.
f^, dm^
7
dj.in
d>n
(181) ^
'
together with v as those which are to remain constant in differentiation, the value of
be at
least as small
Now we
determined
the limit
differential coefficients, as
any of these ways, can have a negative value within of stability, and that some of them must have the value zero
Therefore, in virtue of the relations just established
at that limit.
one at least of these differential coefficients determined by considerinoconstant the quantities occurring in the numerators of the others
together with
y, will
zero.
But
if
value zero,
all
For
if
\drnjt^
for example, has the value zero,
V, fii,
nni
'
by
we may
yUj,
;^,
brium.)
Xow 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
tial coefficients
formed
the fractions in
analogy of (182), i. e., formed from (181) by taking as constants for each the quantities in
after the
the numerators of the others together with y, will in general have the value zero at the limit of stability. And the relation which
characterizes the limit of stability
setting
may
be expressed, in general, by
Such
172
J.
W. Gihhs
is known, may be reduced to the form of an equation between the independent variables
Again, as the detei'minant (173) is equal to the product of the differential coefficients obtained by writing d for A in the first
members
may be
expressed by
?;,
?,,
will be altered
by
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.
d^A
fJn
1
=0,
(183)
that
is,
that
drV
(184)
i,
F\
jWn^l
. .
or
by
(98), if
we regard
if,
yw^,
yw
td^\_
XdiJ^^I
(185)
In like manner
we may obtain
d^p ~dP
d^p
d^p
(186)
Any
eral, as
one of these equations, (185), (186), may be regarded, in genWe may be certain the equation of the limit of stability.
that at every phase at that limit one at least of these equations will
hold true.
GEOMETRICAL ILLUSTRATIONS.
Surfaces in lohich the Composition of the Constant.
In vol.
ii,
Body
represented
is
p.
method
is
described of
J.
W. Gibhs
173
by rectangular
kind of funda
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
three,
any one of the sets (99)(103) are reduced to which may be represented by rectangular coordinates. This will, ho\vever, afford but four different methods, for, as has already (page 150) been observed, the two last sets are essentially equivalent
described in the preceding volume has certain advanit
may
more advantageous to select a method in which the properties represented by two of the coordinates shall be such as best serve to identify and describe the difi*erent 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 coordinates and the potential by the third. (See page 143.) 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
between volume,
entrojjy,
and
energy.)
If
we
give
C, which then becomes equal to //. Comparing the two methods, we observe that in one
vz=zx,
i]
= y,
z,
174
J.
W. Gibhs
The
surfaces detined
v7]e
distin
guished as the
surface,
tpt surface,
of the substance to
which they
In the
relate.
t2>'C
point
through which pass three different parts of the surface represents a triad of coexistent states. Through such a point will evidently pass
by the intersection of these sheets taken two The perpendicular projection of these lines upon the pt plane will give the curves which have recently been discussed by ProThese curves divide the space about the projecfessor J. Thomson.*
the three lines formed
by two.
which
may
be distinguished as
follows:
Let
C^'',
?*^\
2>
C^"^'
and
by the three
^(n<KX)<^(S)^
in the
next space, separated from the former by the line for which
^(r)<^(.?)<^(X)^
(192)
in
by the
line
for
which
(193) (194) (195)
(196)
^(S)<^(r)<^W
in the fourth
^^^
in the fifth
^(^)<?(^><?(^
?(<^(^) <?(*).
'C,
in the sixth
The
is
which
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.
values of
t,
But the
states
represented
by
the intermediate
may
by
of
the highest.
The
differences
^^^^
?^''>,
etc.
represent the
amount
work obtained
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
* See the Reports of the British Association for 1871 and 1872
;
and Philosophical
Magazine,
J.
Substances.
175
This will in general cut the double line formed by the two sheets to which the symbols (X) 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
reversible
path
state
for the
states.
The geometrical
stability of
any
may be
by applying
is
the principles stated on pp. 156 ff. but a single component. The expres
t' 1]
\ 2)'
ji'
rn^
(197)
is in
we
con
may
'Q'Q'[{tt')n{2yp')v,
(198)
which evidently denotes the distance of the point {t',p\ C') below the tangent plane for the point {t,p, t), measured parallel to the axis of
t,.
Hence
if
the tangent plane for every other state passes above the
If
any
of the tangent planes pass below the point representing the given
state, that state will
be unstable.
Yet
it is
For, as has been observed on page 160, 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.
represented
plane p=.Q
for
a point in the surface on the positive side of the will be unstable only when there is a point in the surface
t,
by
which t and jo have the same values and a less value. It follows from what has been stated, that where the surface is doubly convex upwards (in the direction in which is measured) the states repre'Q
surface
is
either of its principal curvatures the states represented will be unstable in respect to adjacent states.
it is
the number of component substances is greater than unity, not possible to represent the fundamental equation by a single surface. have therefore to consider how it may be represented
When
We
number of surfaces. natural extension of either of the methods already described will give us a series of suifaces in
by an
infinite
176
J.
W. Gibhs
is
tjyt
surface for
varying as we pass from one surface to another. But for a simultaneous 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 ov p constant in each surface.
Surfaces
sented
is
v:ihich
its
When
per
The body
is
mj, mg,
the value of
m,
f
mg
in the
same straight
line.
If
we suppose masses
m3
the height unity, the distances of the point from the three sides will
be equal numerically to m^^ mg, ni^. Now if for every possible phase of the components, of a given temperature and pressure, we 3^ plane which represents the compolav off from the point in the JTsition of the
Z and (when m^ j "'2 "h^s ^= 1)5 ^^ points form a surface, which may be designated as the
m^m2"^3? surface of the substances considered, or simply as their In like manner, m'Q surface, for the given temperature and pressure.
two component substances, we may obtain a XZ plane. The coordinate y may then represent temperature or pressure. But we will limit our
when
curve, which
we
nii;.
surface for
n =r 3, or the m'C curve for n r= 2, regarded as a which varies with the temperature and pressure. As by (96) and (92)
surface, or curve,
and
(for constant
dm^
f /U2
dm^ +
yWg
dm^,
which these
letters
if
we imagine
relate,
and denote by
the plane,
J.
TK Gibbs Equilibrium
oj'
Heterogeneous Substances.
177
/,', /^a? "^3? the distances of tlie foot of this ordinate from the three sides of the triangle P^ Po P3, we may easily obtain
and by
'Q'
= yWjm,' +
//j,
fx
m'
f //g w^a',
(199)
which
Ave
may
There
^^^ ^" general, the ordinate ^^^ ^^^^ A'sfor any point in the tangent plane is eqvial to the potential (in the
phase represented by the point of contact) for a substance of which
is
the composition
indicated
by the
(See
page
149.)
Among
may be formed
of S^,
jS^,
and
S^, there
tion, or
which are capable only of a single kind of variation. These 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 determine a series of jDotentials of which only two
will be represented
will
be independent.
which
will
be equal to
The
a
common
tangent plane.
is
situated
on the edge where a sheet of the surface terminates, it is sufiicient if Or, the plane is tangent to the edge and passes below the surface. when the point is at the end of a separate line belonging to the surface, or at
an angle
in the
edge of a
no part of the
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 and m^, m^, m^ for homogeneous bodies when t and p have any constant values and m^ j mg It will often be ^^5 =: 1. useful to consider the surface which represents the relation between
t.
the same variables for bodies which consist of parts in different but
coexistent phases.
We may
in
The
point which
body
will evidently
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
Trans. Conn. Acad., Vol.
III.
23
January, 1876.
ITS
J.
W. Gihhs
may
which are
This
may be
in
called
surface.
will
consist,
general, of
The
may
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
has a triple tangent plane or one of higher order, the triangle in the
polygon without reentrant angles which includes all the points of contact, will belong to the derived surface, and will represent masses
more phases. surface as thus constructed for any thermodynamic Of the whole pressure, that part is especially imporpositive any temperature and value of for any given values of m,, mg, least ? tant which gives the represented by a point in this part of the The state of a mass m^.of energy would be possible if surface is one in which no dissipation impermeable both to envelop the mass were enclosed in a rigid matter and to heat and the state of any mass composed of S^, S^, S^ in any proportions, in which the dissipation of energy has been comconsisting in general of three or
;
limitations imposed
by such an envelop
as
we
We may
of
dissipated energy.
It is
evident that
it
Y plane coincides
for
is
which the
surface
is
constructed
enero"y,) that
no surface of dissipated nowhere has any convexity upward, and that the
lines for
states
which
it
The general
We
now
proceed to illustrate the use of both the surfaces and the lines
of several particular cases.
by the discussion
Three coexistent phases of two component substances may be is represented by the points A, B, and C, in figure 1, in which from PjPg, toward the left top of the page the toward measured >'^i from P2Q25 ^"^^^ ^2 toward the right from P,Q^. It is supposed Portions of the curves to which these points belong 1. that PjPjj
'Q
J.
W. Gihhs
179
(B),
We
may,
for convenience,
without implying anything in regard to their possible continuity in The parts of the diagram remote from their common tangent AC.
line
of dissipated energy includes the straight line AC and portions and (0). Let us first consider how the diagram will be altered, if the temperQ..
ature
is
re
mains constant. If the temperature receives the increment dt, an ordinate of which the position is fixed will
receive the increment
b
Fig.
1.
'^^'
''^'
If
dt.
(The reader
true of the
AC,
Now
if
we denote by
phase represented by the point B considered as belonging to the curve (B), and by if the entropy of the composite state of the same
jf) will
first to
ature will evidently cause a part of the (;urve (B) to protrude below
the tangent to (A) and (C), which will no longer form a part of the
line of dissipated energy.
three curves (A), (B), and (C), and of the tangents to (A) and (B)
and and
On
entirely
all
by (B)
will
be
imstable.
{if
be produced by
The
effect of a
change of
in a
piessuie
constant
tion of
may be found
manner
The
variaif
any ordinate
will
be
dp or V
dp.
Therefore,
the
volume of the homogeneous phase represented by the point B is a greater than the volume of the same matter divided between the the phases represented by A and C, an increase of pressure will give diagram indicating that all phases of the sort represented by curve (B) are unstable, and a decrease of pressure will give a diagram indi
80
J.
W. Gibbs
eating two stable pairs of coexistent phases, in each of which one of the pliases
is
volumes is the reverse of that supposed, these results will be produced by the opposite changes of pressure.
rehition of the
two
cases which
must be distinguished.
tangent plane
three
;
lies
by joining
the other
in
may
be joined so as to form a
angles.
X
Y plane
(in
which
falls
ABC
in the
quadruple tangent
portions of
l^lane,
sheets.
Fig.
2.
Fig.
sented in the
figuie
by ruled
ABC
by
manner not
such that
if
J.
W. Gihhs
181
Such a mass, if exposed to constant temperature and pressure, would be in neutral equilibrium. A point in the developable surfaces repre
mass of which the matter is divided between two coexisting 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
sents a
C which
is
If the first
(i.
is
e.,
the
the
belongs) to sep
and a decrease of temperature, will cause a part of the sheet (D) to protrude through the plane tangent to
situated entirely above
it,
These
effects will
is
the volume of the same matter divided between the phases A, B, and
C.
If the
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.
will
And
if
these effects
the homoge
volume.
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
by the disappearance
of the point D.
But when
3.
the sheet (D) protrudes below the plane tangent to the other sheets, the surface of dissipated energy will take the form indicated in figure
by
182
J.
W. Gihbs
But wlieu the points of contact with the quadruple tangent plane which represent the four coexistent phases can be joined so as to
form a quadrilateral
4)
portions of the four sheets of the primitive surface which are tangent
to
it,
Fig. 4.
Pig.
5.
tangent planes rolling upon the four pairs of these sheets which corres
pond
To determine
by
the gen
energy,
let
Among
all relate to
there
is
is
one which
which
the
Now
first
is
of these states
is
e., if
heat
to the second
and
pressure,)
which we
may
suppose
(D),
to
(B),
(D), and
(C),
(C),
to
rise
above the
(A),
(C),
tangent
to
(A),
and
(B),
and
to
and (D), in the vicinity of the point I. The surface of dissipated energy will therefore take the form indicated in figure 5, in Avhich there are two plane triangles and five developable surfaces besides
portions of the four primitive sheets.
will give a difierent
diminution of temperature
dis
sipated energy.
into
The
ABCD
lU).
will
in
this case
break
The
effects
produced by
J.
W. Gihhs
183
the difference
states repredistin
two
sented
by
we may
may be
at isolated points or
So
of two component
And
in the
it
will
generally be
the reader to
make
in in
two components, shall remain possible, has already been deduced by purely analytical processes.
We will
The
cal composition,
and
first,
of components
is
two.
represented
One
of the
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
curves will in general
;
ponent
may
if the proportion of either comvarying the temperatui'e or pressure, we cause the upper curve to protrude below the other, or to rise
is
increased.
By
(relatively)
entirely
above
it.
we may
easily determine
which result would be produced by an increase of temperatiire 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 Avhich we have
considered before, but there ceases to be any such pair of coexistent The same result has already been obtained analytically on phases.
184
J.
W. Gibhs
page
155.
But on that
t
theie will
be two
and
p, as seen in figure
AA'
repre
sents vapor,
liquid, a liquid
(represented by)
a vapor A,
B may
same temperature and pressure) a liquid B' in contact with a vapor If we compare these phases in respect to A'.
and
(at the
their composition,
Fig.
6.
we
vapor
is
component, and
are
Therefore,
if
these liquids
If
made
the boiling
BB'
to each other,
AA', until the curves are tangent become identical in nature, as also
t
per
the
unit of mass, the vapor will then agree with the liquid.
But
if
curve BB' (which has the greater curvature) represents vapor, and
AA'
make
the liquids
and A'
more
in composition.
cated 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
just considered.
The upper
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 dissi
pated energy will include a portion of each sheet of the primitive surface united by a ringshaped developable siirface.
If the sheet
liquid,
and
the other sheet vapor, the boiling temperature for any given pressure
will be a maximum, and the])ressure of saturated vapor for any given temperature will be a minimun, 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 liave the same composition, intersect
J. TT.
Gihhs
85
seen from
below
from
may he
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 tigure
primitive surface, and
united by the
ATB, ETF are parts of one sheet ol the 7. CTD, GTH are parts of the other. These are developable surfaces BTC, DTE, FTG, HTA. Now
variation of tempei'ature or pressure.
If the
we may make
the other
sheet to which
by the proper
ATB, ETF
belong
is
be merged
surfaces
developable
BTC, DTE, and also FTG, HTA. (The lines CTD, BTE, ATF, HTG will
But
if
CTD
BTC,
ATH, and
It is
also
DTE, FTG.
is
not a case of
maximum
or
minimum tem
maximum
minimum
when
two.
In this case, the primitive surface must touch the same plane
same straight
line.
of the primitive surface to which these points belong as the sheets (A),
(B),
is
The
(B).
it
may
or
it
it
may
not intersect
it
at the point of
above the developable surare unstable in regard face, (unless it represents states which changes,) and the surface of dissipated energy to continuous will include parts of the primitive sheets (A) and (B), the developdoes not,
must
lie
which
it
Now,
the tempera
ture or pressure
varied so as to
III.
make
24
186
J.
W. Gihbs
developable surface formed on the sheets (A) and (B), the surface of dissipated energy will be altered in its general features only by the
(C).
if
altered so as to
make a
through the developable surface formed on (A) and (B), the surface of dissipated energy will have the b form
will
indicated in figure
include two
8.
Tt
plane triangles
ABC
"
part
CC
last
two being
surface
it
But
if,
when
the
primitive
is
plane intersects the developable surface formed upon the other sheets
(A) and (B), the surface of dissipated energy will not include this
develojjable surface, but will consist of portions of the three primitive sheets with
two developable
surfaces formed on (A) and (C) and These developable surfaces meet one another at
tri2)le
make
the sheet
de
sink
relatively to the
and
face
Fig.
9.
the general features of the surof 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.
will give a
J.
W. Gihbs
Equllihriunh of Heteror/eneous
is
f'iuhstances.
187
ABC, A'B'C
planes, a portion of the sheet (A) on the left of the line aAxV'a', a portion of the sheet (B) on the right of the line bBB'b',
two separate
portions
aACc
and a'A'C'c' of the developable surface formed on (A) and (0), two separate portions bBC;^ and b'B'C';/' of the developable surface formed on (B) and (C), and the portion A'ABB' of the developable surface formed on (A) and (B).
From
it
appears that
is
(in
general) the
maximum
or
minimum
for
mum
or
minimum
of
on page 150.
the nature of the surface of dissipated energy have been only occasionally mentioned, as they are often far
more
distinctly indicated
by
It will
be observed that
a knowledge of the lines which divide the various dilFerent portions of the surface of dissipated energy and of the direction of the rectilinear elements of the developable surfaces, as projected
upon
the
tn'C,
surface in
space,
is sufficient for
and composition 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 sistances to change.
CRITICAL PHASES.
It
re
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 compounds of variable composition without change of temperature or
* See Dr. Andrews
''
On
188
J.
W. Glbbs
For
if,
pressure.
at
liquids
mg
less
than
and in any greater than h, 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 qiiantity of the third to form a stable mixture, it may easily be seen that two coexistent mixtures of the three liquids
may
ture and pressure remaining the same, from initial phases in each of
which the quantity of the third liquid is nothing, to a terminal phase 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
in
regard to phases which are unstable in respect to conthe coexistent phases and the critical phase are
But
if
from the
will in
critical
changes
no respect
and adjacent phases, the liability to such between the critical and
it
may
ing discussion, phases in the vicinity of the critical phase will generally be called stable, if they are unstable only in respect to the
Let us
first
consider the
number of independent
is
variations of which
If
capable.
we denote by
the
number
we
critical
phase,
we
by the
If
we now vary
have
n l quantities, we shall
stant a
for the
new
set
new
Now
for every
J.
189
in the first,
and must be
but
differs
infinitely
from the
first.
;/
We
we vary
arbitrarily
of the quantities
//g?
/^n,
as deter
mined by a
critical phase,
we
i.
e.,
a critical phase
is
capable of
The quantities t, p, /v^, fj.2, A'n, have the same values in coexistent phases, but the ratios of the quantities i],v,m^,m^,,
.
two
.
m,
two phases. Or, if for convenience we compare equal volumes of tlie two phases (which involves no loss of generality), the quantities r/, m^, m,2, ni will in general have different values in two coexistent phases. Applying this to coexisare in general dift'erent in the
. . .
we
immediate vicinity of a
ties
t,
critical phase, if
p,
/<,, //g,
Mn, are
the
compared
This con
?/,
m^, mg,
m.
we may
(j
characterizes, as
=0,
(200)
we have
In fact,
if
we give
by
to the quantities
^,
yWj, yUg,
/<_i
constant
a series
it
values determined
of values increasing from the less to the greater of the values which
we determine
since
it
has the same value in the two coexistent phases, but not a uniform
if it
had, Avhich
is
theoretically im
these phases
would be coexistent)
if
must be a decreasing
Therefore,
function of
^,
or of m,
v also
is
supposed constant.
the series must contain phases which are unstable in respect to con
tinuous changes.
phases
(See page
68.)
And
may
phase, the
190
./.
W. Gibbs
have similar properties with reference to stability 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
Critical phases
critical
phases which
leave out of
we
account the
in respect to
which the
critical
phase
is
The
ties
^,
by giving to n
ol the quanti
jo, yUj,
'
Mn
t.he
part
in
Hence,
a critical phase
. .
J^n
remain constant,
to discontinuous changes.
rn
Therefore,
yu is
an increasing function of
when
t,
v, jj^, ^Iq,
pini
any
critical phase.
But
phase, the following conditions must also hold true at that phase
(^'^1
=0,
^0.
V,
'
(20,)
\dm^Jt,
(202)
satisfied.
may
capable of
n1
inde
pendent variations. We are not, however, absolutely certain that equation (200) will
always be
satisfied
in
by a
critical phase.
For
it
is
denominator
are constant.
refer to
the fraction
may
some
different
tial coefficient
we may siippose the subscript n to component substance, or use another differenof the same general form (such as are described on
In such a case,
limits of stability in respect to con
making the corresponding changes in (201) and We may be certain that some of the formulae thus formed (202). But for a perfectly rigorous method there is an advanwill not fail.
J. TT^
Gihhs
101
tage
in the use of
//,
mj,*^,,
as
independent variables.
The
may be
will
ii^, //o,
...//
i?+t=^.
in
which Rn+x
^^enotes the
same determinant
on page 169.
critical
^,
A'n
volume,
viz.,
"n+ldtf^^I^^l dm.
dt}
_j_
'
dli^,
^j^^^
dtrir,
dm^
'
(204)
cannot become negative when a 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
c?//,
dm,^^ etc.
sion (204) has the value zero, \in of the equations (172) are satisfied.
This
may be
expressed by an equation
aS'=0,
(205)
in
which the constituents are the same as in 7?+,, except in a single horizontal line, in which the differential coefliicicnts in (204) are to be substituted. In whatever line this substitution is made, the equation (205), as well as (203),
aS
which
denotes a determinant
in
we
choose
^,
/),
Wj, Wg,
wi as
write
TJ for
the determinant
dH_
c?m,2
^?^?_
dm^dm^
dm^_^dm,^
dn
dntydm,^
dn dm 2^ dH
formed from
this
dn
dm,^_^dm^
(206)
d^^
drn^dm
_dH
by substituting
for the
and
dU
dm?^
dU
dn/in^^
^
''
U=
It results
0,
F=
0.
(208)
immediately from the definition of a critical phase, that an infinitesimal change in the condition of a mass in such a phase
192
J.
W. Gihhs
may
in
(i.
e.,
is
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 If we consider a change in the mass to be deterinfinitely small.
(///,
dv,
dm^,
dm 2,
dm,
it
is
evident
that the change in question will cause the mass to cease to be homo
^^1 a,j+
d?]
it
^i^^i
dv
dv+
^"' dm,,
dm
c7m + ^^^ dm
(209)
For if the mass should remain homogeneous, would become unstable, as Hn^i ^voukl become negative. Hence, in general, any change thus determined, or its reverse (determined by dm the same values taken negagiving to c?//, dv, dm,, dm2, The condithe mass to cease to be homogeneous. will cause tively), satisfied with reference to dt^, dm,, dm^, must be dv, which tion neither the change indicated, nor the order that in dm, of homogeneity the mass, is expressed by destroy the reverse, shall zero. expression to equating the above But if we consider the change in the state of the mass (supposed to remain in a state of dissijiated energy) to be determined by arbitrary
has a negative value.
. . .
be entirely
different.
For,
if
will consist of
two
n of the
fore, for
quantities
/^n
will
be independent.
There
must in general remain homogeneous. But if, instead of supposing the mass to remain in a state of dissipated energy, we suppose that it remains homogeneous, it may easily be shown that to certain values of w j 1 of the above differentials 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,
is
In general, however,
or
n of the quantities p,
t,
/.i
mined
But
if less
J.
W. Gibhs
193
the latter
tlie same together with cerm^, m,, or arbitrary functions of quantities, have the same values as at a critical phase, so
in
by considering separately the n=zl and n 2. If a mass of invariable composition is in a critical state, we may keep its volume constant, and destroy its homogeneity by changing its entropy (i. e., by adding or subtracting heat probably the latter), or we may keep its entropy
illustrate these relations
We
may
cases in which
its
homogeneity by changing
its
we keep
its
pressure constant
we cannot destroy
its
any thermal action, nor if we keep its temperature constant can we destroy its homogeneity 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,
its
if
is
main
homogeneity may be destroyed by a change of volume or pressure. In both these cases it is sup^^osed 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
tained constant,
Or,
if
a mass consists of
two coexistent
the mass
is
maintained constant,
it
will not
be possible by mechanical
or thermal means, or
by changing the
ments of
this
whole mass. The stateparagraph and of the preceding have reference only to
infinitesimal changes.*
*
of a
A brief
abstract (which
came
"
memoir by M. Duclaux,
Sur
III.
25
February, 1876.
194
.7.
W. Gihhs
ON THE VALUES OF THE POTENTIALS WHEN THE QUANTITY OF ONE OF THE COMPONENTS IS VERY SMALL.
If
we apply equation
we
obtain
(97) to a
homogeneous mass having two indeaS'j, and make <, jo, and mj
,ip\
Therefore, for ^21=0, either
+,Jp)
^0.
(2,0)
>) (21 ^
'
(212)
ydm^Jt,
p,
m,
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,
ponent
true
irt,
/Sg,
we
shall
general as
any other variable comequation But ^2=0. (212) cannot hold thus applied. For it may easily be shown (as has and
in respect to
have
been done with regard to the potential on pages 148, 149) that the value of a differential coefficient like that in (212) for any given mass,
^S', (to which m^ and }.i relate) is determined, is independent of the particular substance which we may regard as the
when
the substance
if
when
by S^ has been
restriction,
In fact,
true of
is
any phase which is stable in regard to continuous changes and in which ^3=0, if nn.^ is capable of neggiive as well as positive For by (171), in any phase having that kind of stability, /<, values. is an increasing function of m^ when t^ p, and m^ are regarded as Hence, /<j will have its greatest value when the mass conconstant.
sists
wholly of
/6'j, i.
e.,
when mo^O.
Therefore,
if
mg
is
capable
m^ = 0.
See page 177.) But if m^ is capable only of positive values, we can only conclude from the preceding considerations that the value of the differential
of potentials in the mC curve.
coefficient in (211)
cannot be positive.
Nor,
if
we
./.
TV.
Gihbs
195
coeffi
To
fix
our ideas,
let
us suppose
particin a
that
*S^j
*^'^^t
(either
anhydrous or any
ular hydrate).
The addition
state capable of equilibrium with vapor or with ice, will destroy the
possibility of such equilibrium at the
pressure.
is
The
that
liquid
ice,
brought
//,
under such circumstances, which shows (the potential for water in the liquid mass) is diminished by
in contact
with
it
salt,
when
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.
tained constant.
Now
there seems to be no
We
effect of this
should rather expect that, for small quantities of the salt, an kind would be proportional to its cause, i. e,, that the
would have a finite negative value for That this is the case with respect to
salts is
distinctly indicated
by the
experiments of Wtillner* on the tension of the vapor yielded by such solutions, and of Riidorfff 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
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
in
true.
But
is
this case
which mg
may
be
illus
trated
by
For
this
purpose
let
S
IS.y
denote a hydrate of the salt which can be crystallized, and let denote water, and let us consider a liquid consisting entirely of
pi'essure as to be in equilibrium with In such a liquid, an increase or a diminution of the quantity of w^ater would alike cause crystals of S^ to dissolve, which
crystals of
requires that the differential coefficient in (211) shall vanish at the particular phase of the liquid for which m^ 0.
in
(1858j, p.
p.
564.
Pogg. Ann.,
196
J.
W. Gibbs
and
tor
any con
of
that
may be regarded
the values of
t,
as having the
same
constant value as
when m^
0,
p, and
being un
changed.
If
we
Then
we have by
(210), approximately,
1.
e.,
(214)
If
we
/^2=^4
j5 like
1og^,
(215)
will
have a positive value depending only upon the temperaAs this equation is to be applied only to cases in
is
ni^,
we may
as constant,
and write
/i2
= ^log^,
(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 argument will be in no respect invalidated, if we suppose the composition
of the
tities
body
and
will
temperature and
the body
is
composed.
If
iS^
/a^,
if
J.
W. GihbsEquilihrium of Heterogeneous
if
Snbstances.
197
are
Hence,
/S,
.
body
as
the quantities of the latter being very small and S,,^ compared with the quantities of the former, and are incapable of
.
.
S,i,
/S'^.,
negative values,
potentials for S,
tainties
we may
.
by equations (subject of course to the uncerof the assumptions which have been made) of the form
. .
tS^.
/^;,=
(217)
198
these
cules
(T.
JV.
Gihbs
may
be more complicated.
differ in the
by mole
which
not in the kind of matter, nor in the proportion of the different kinds.
In
still
which
in
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
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 example given above, the temperature must not be raised beyond a certain limit, or molecules of hydrogen and of oxygen
body
may be
The
in the con
bodies containing the same matter and in the same thermodynamic state as determined, for example, by pressure and temj^erature, as the
These which depend upon the which the molecules are combined to form sensible masses.
different sorts are varied.
increase in the
number of
variables in the
but they
may
is
of
the independent variables, as, for example, when we have several in, one different values of ? for the same values of t, p, m^, in^,
. . .
perhaps being for a gaseous body, one for a liquid, one for an amorphous solid, and others for different kinds of crystals, and all being
invariable for constant values of the above mentioned independent
variables.
B\it
it
by the
quantities of
thermodynamic
increase in the
if
number
we should
mixture of
J.
Substances.
199
vapor of water and free liydrogen and oxygen, which we have just
considered, to a point at which the numbers of the] different sorts of
and the total quantities of hydrogen and of oxygen which are present,
the fundamental equation of such a mass would involve but four inde
pendent 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 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
"Q
body
as determined
by
its
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 the variations of which the body is capable.* Such cases present no
especial
difliculty
;
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
concerned, represented
Yet among the the various phases of the kinds of matter by the different sets of values of the variables
fundamental
eqiiation, there is a certain class which These are the phases for which the entropy value for the same matter, as detei*mined by the
which
has a
satisfy the
maximum
let
ultimate analysis of the body, with the same energy and volume.
fix
To
our ideas
aS\,
.
.
S^
and the
ultimate components S,
quantities of the former,
It is evident that w?
. .
. .
S,,\
. .
and
.
let
w^^j,
m^ denote the
and
. .
?,
homogeneous functions of the first degree of r>^,, 7; and that the relations between the substances aSj, S 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 comm.,^
are
lute sense.
* The terms proximate or ultimate are not necessarily to be understood in an absoAll 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.
200
J.
W. Gibhs
ponents.
The phases
?;
is
for constant
values of
w,
is
C
m,
7n,,
or,
as they
m,
^,
ni,,
.
or for which
is
of
jo,
m,
m,,.
readily determined
tain the quantities
The phases which satisfy this condition may be when the fundamental equation (which will conm^ or yUj, m^, Indeed it is //,) is known.
.
.
. .
we may
phases by substituting
yUj,
/<
These phases
may
That we which 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.
are considering, phases of dissipated energy.
It is characteristic of these
phases that
we cannot
of i
in
any
real
its
mass
volume of
Hence,
the energy or increasing the entropy of some other system. if the mass is large, its equilibrium can be but slightly dis
turbed 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 compoits temperature and pressure
not such as to constitute a phase of dissipated energy, it may be mass by the contact of a very
small body.
contact
Indeed
it is
by such
may
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
components of the
first,
which there
lence in respect to their ultimate analysis), independently, and without passive resistances, but for which the phase is completely deter
J.
W. Gibbs
its
201
mined by
By
the
is
8^ independently
it
shall
be
by
change of
all
An
some other kinds of change two bodies can remain in contact preserving the properties which
have been mentioned.
may of course be made for prevented by the occurrence of in other words, it is assumed that the
The term
sidering.
we
are con
When
out limitation
body has the property of reducing another, withwith respect to the proportion of the two bodies, to a
in
may
be called
a.
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
is
entirely determined
its
by
its
ultimate compo
by the
quantities
just mentioned,)
be completely defined by the quantities of certain proximate components with the temperature and pressure, and
the matter of the mass
reversible from
may
may be brought by processes approximately 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 containinoa smaller number of independent variables, which has reference solely
;
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
to the final phases of equilibrium.
it
phases alone.
Now,
of the rapidity of the molecular changes, the question naturally arises whether in cases in which we are not able to distinguish such trausiTrans. Conn. Acad., Vol.
III.
26
February, 1876.
202
J.
W. Gihbs
may
have a theoretical
significance.
If so,
assist
may
of experimental demonstration.
is
and pressure, and we have composed of a greater number ?^' of proximate components, which are therefore not independently variable (while the temperature and pressure remain constant), it seems quite possible that tlie fundamental equation of the body may be of the same form as the equation for the phases of dissipated energy of analogous compounds of n' proximate and n ultimate components, in which the proximate components are capable of
able components, with the temperature
is
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 constitution of the
body.
Such considerations seem to be especially applicable to the very 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 produced by these variations are permanent in their nature, while at other
common
temperatures and pressures, likewise regarded as constant, the quantities of these proximate components are not capable of independent
variation,
and the jDhase may be completely defined by the quantities There of the ultimate components with the temperature and pressure. condipressures, temperatures and a may be, at certain intermediate tion with respect to the independence of the proximate components
intermediate in character, in which the quantities of the proximate
components are independently \ariable 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 mentioned has any necessary connection with
state.
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 143,
if
m,, m^,
m,
/^j, /<2,
yWn
are
J.
W. Gihbs
Equilihriun)
of Heterogeneuus Substances.
203
Therefore,
equations will agiee 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.
by supposing the values which the quantities of the ultimate components are constant to be represented by rectilinear coordinates.
illustrate these relations
in
We may
for a
of
t,
I),
and
mass
Where
by
t
will not
and the points representing connected values of <, jo, and I will form This solid will be bounded in the direction opposite to that a solid. is measured, by a surface which represents the phases of in which
'Q
dissipated energy.
sented
may
(for
In a part of the figure, all the phases thus reprebe permanent, in another part only the phases in the
bounding
figure
surface,
and
may be
is
no such solid
experimentally
any phases
of which the
existence
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.
be
if
different
sheets
representing liquid
and
but
we
We
fundamental equations
of gases, have an example of the derivation of the fundamental equation for phases of dissipated energy (with respect to the molecular
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
in
impermeable to matter and to heat, and in other respects, except regard to gravity, to make the same suppositions as on pages 115,
116.
The energy
now
consist of
two
parts, one of
204
./
W. Gihbs
position in space.
Ds the
intrinsic
energy of
this element,
A
;
its
plane,
will
fDe\fghJ)m,
in
all
and
d/De + dfg h Dm ^ 0,
the variations being subject to certain equations of condition.
(220)
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 quantiWe shall supties of each of the component substances is constant. equations of condition, other and that the pose that there are no independently variable components are the same throughout the
whole mass
;
and we
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
from any initially existing in the same vicinity. Dm denote the entropy of the element Let Z>//, Z>y, 7>mj, Z>m, its volume, and the quantities which it contains of the various
.
components.
Then
Dm = Dm^
and
Z>m,
(221)
dDm dBm^
Also, by equation (12),
+ SI>m.
.
. .
(222)
6 Da
6I)ij
dJJv
+ /ij SBm^
\ ,u
6J)m.
(223)
By
may be
ft 6Dri
fp 6Dv
+//', 6Bm^
/// SD^n^
(224)
Jrfg Sh
Dm
\/gh
SDm
J^fgh dDm ^ 0.
we must
Now
affect
it
will
diflf'erent
have, sepa
rately,
ftSDtj^O,
if
fdDrf=Q;
(225)
../.
W. Gibbs
Equilibriuiii of Heterogentoiis
fp 6Dv \fg 6h Dm ^ 0,
is
fSubstaitces.
205
(226)
if
mivaried
dlJra^
dihn
+ fgh
^ 0,
if
/6Dm = U n
j
y> 6Dm^ + f<i h 6JJrn ^ 0, if J'6lJni = 0. ) From (225) we may derive the condition of thermal equilibrium,
t
(227)
= Const.
(328)
Condition (226) is evidently the ordinary mechanical condition of equilibrium, and may be transformed by any of the usual methods.
We may,
at
motions as miglit
of indeterminate form.
we denote by
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 6dv + fg 6h dm ^ 0,
in
(229)
which the integi'ations include the whole contents of the tube. Since no motion is possible at the ends of the tube,
6v) =z
0.
(230)
we denote by y
fg 6h dm =fg ^
By f6v
Therefore, since 6v
is
Sv y dv =^fg y Sv dh.
(231
may
{dp
\
g y dh) ^ 0.
arbitrary in value,
dp=~gydh,
which
will hold true at
(233)
any point
taken with respect to the direction of the tube at that point. Therefore, as the form of the tube is indeterminate, this equation must hold true, without restriction, throughout the whole mass. It evialone,
dently requires that the pressure shall be a function of the height and that the density shall be equal to the first derivative of
this function, divided
by
g.
all
Conditions (227)
equilibrium.
contain
that
is
To
that
/^i
+ ff^
Const.
(234)
Mn
+ 9^=.
Const.
206
J.
W. Gihhs
The
expressions
pi^,
//
several components,
"the
mass about that point. We may avoid, all quantities and the potential of the force of gravity,
the former, indicated
we have called and which are entirely nature and state of the confusion between these
if
when
by equations
may
W/ten a fluid mass is in equilibrium under the influence of gravity^ and has the same independently variable cotnpofients throughout, the intrinsic potentials for the several components are constant in any
given
level,
ence of
the values
at two
different levels, being equal to the work done by the force of gravity xohen a unit of matter falls from the higher to the longer level. The conditions expressed by equations (228), (233), (234) are
in
phase with any previously existing about the points where they may be formed. The possibility of such formations at any point is evidently
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 128134.
But equations (228), (233), and (234) are not entirely independent. For with respect to any mass in which there are no surfaces of discontinuity (i. e., surfaces where adjacent elements of mass have finite
diiFerences of phase), one of these equations will
the others.
Thus by
(228)
and (234), we
may
which
tion
vdpg {m
or
+ m) dh
(235)
(236)
dp=  gy dh
which will therefore hold true in any mass in which equations (228) and (234) are satisfied, and in which there are no surfaces of discon
But the condition of equilibrium expressed by equation of discontinuity; (233) has no exception with respect to surfaces will be necessary occur, it surfaces therefore in any mass in which such by equations expressed relations for equilibrium, in addition to the
tinuity.
(228)
shall
at these surfaces.
This superfluity in the particular conditions of equilibrium which we have found, as applied to a mass which is everywhere continuous
./.
W. Gihhs
207
in phase, is
due to the
is
made
tlie
elements of volume
these elements
different
Now,
as the
components may move in different directions when the state of the system varies, it is evidently im])Ossible 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
elements fixed
tinuity, this
and therefore
it
would be allowable
plan.
to
make
these
in space.
If the given
But
if
surfaces of discontinuity,
will
mass
by
be necessary to add to
oixr
general con
elements of
surfaces,
necessity
which
is
avoided
if
we
we can then
sup
pose that each element remains always on the same side of the sui'face
of discontinuity.
Method of
It
tJie
elements of
may be
how
of equilibrium
may
be obtained
if
we
volume
If
as fixed in position
and
size,
possibility of finite as
we
sic
by such
finite differences
of phase,
we may
in the
form
(237)
fdDe+fABE,
in
which the
finite
first
infinitesimally varied,
all
variation.
We may
we do
we may use T 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
and
in intensity,
fT6DmfTADm.
(238)
208
J.
W. Gibbs
We
J'SDe
(239)
be
fSBi)
.
\fAI)i]
,
=
.
0,
,
(240)
0,
.
f8Dm + fADm =
.
.
[
)
(241)
J'6I)m
+ fADm^ =
0.
We
may
by subtracting these equations, multiplied each by an indeterminate constant, from condition (239). If we denote shall obtain iff, we these indeterminate constants by T^ Jfj,
tions of condition,
. .
.
/
The
SDi
T 6Dm
T6Dt]
Jf, 6
Dm
Jlf 6Dm^
(242)
lfdDm^o^
in
and
finite,
independent of the equations of condition (240) and (241), and ai'e only subject to the condition that the varied values of De, Z>//,
Dm
I,
of phase.
But
as
ence both a
finite
by a certain change we do not suppose the same element to experiand an infinitesimal change of phase, we must have
T6I)ij  J/, 6I)m^ ...
 3I6J)m^0,
(243)
...
 MADm^0.
(244)
in virtue
{tT)
for
SD,f
(yu,
 r M,) SBm^
+
{/J
r
M)
SDm ^
(245)
which
it is
T,
(246)
V*
(247)
//r=jf.
* The gravitation potential is liere supposed to be defined in the usual way. But if were defined so as to decrease when a body falls, we would have the sign + instead of in these equations; i. e., for each component, the sum of the gravitation and
it
intrinsic potentials
J.
W. Gihhs
209
Condition (244)
form
J/) JX>y?^0; (248)
(r+
JI)ni^ ...
/JJI)m^0.
aie
(249)
distin
Be' 
Dtf
/'
^'/^^
0,
(250)
which
may
if
be reduced by (93) to
De'
tJJif
7>>j, ...
iiJJniJ
+ pDv^O.
(251)
Now
(for the
Dv is
Dt\
Drf, lJm^\
J)m^
.
to be determined
same element of volume) by the phase existing on the other As #,//,,.. // have the same side of tlie surface of discontinuity. values on both sides of this surface, the condition may be reduced by
(93) to
p'Bv +pBv^O.
That
is,
(252)
Applied more generally, (251) expresses the condition of equilibrium with respect to the possibility of discontinuous changes of phases at Bv, the condition may also be written any point. As Dv'
Ba'
 tBif +pBv' 
yu,
Z>m,', ...
.
. .
u^BmJ^O,
.
(253)
yw have values determined which must hold true when t, p, /u^, BmJ have by any point in the mass, and Be', By', Bv', Bm^',
.
.
values determined
the mass
is
by any possible phase of the substances of which composed. The application of the condition is, however,
128134.
It
may
shown (see pages 160, 161) that for constant values of ^, /.i^, //, and of Bv', the first member of (253) will have the least possiBm' are determined by a phase ble value Avhen Be', />//, Bm^', for which the temperature has the value t, and tlie potentials the
. . .
values //,,...
//.
It
will
be
sufficient, therefore, to
it
consider the
may be reduced
(254)
by
(93) to
p^p'^0.
That
is,
phase of the same components, for which the temperature and the
Tbans. Conn. Acad., Vol.
III.
27
April, 1876.
210
J.
W. Gibhs
when
be at
not satisfied,
if
e(uilil)riuni
subsists,
it
will
Hence, the phase at any ])oint 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),
completely deter
any other point and the difference of the values of the gravitation potential for the two points.
at
For a
we may write
V
=a
t,
d8
^c
dt,
a and
denoting constants.
By
integration,
we
=CJ+E,
in which ate t and
If
by these equations we
elimin
from
(11),
we obtain
de =i
or
f^ di]
,
a
V
,
sB
c
dv,
ds
c
v^
dv = di) a be written
T)
The
may
z=i
in the
form
a log V
H,
the
where ^denotes a fourth constant. energy of a unit of the gas for ^=0
its
volume
for t=z\
and p=.\
volume.
11
,
of the equation to
we substitute 
in
V m
for
f,
//,
v. respec^
J.
W. Gihbs Biquilibrmm
e
oj^
Heterogeneous Suhstcmces.
211
c loo"^
Em cm
If
^^ H ^
a loo.
in
"u
(2o5)
^
'
,.
_v
This
is
invariable composition.
be observed that
pearing
in
solely as constituting
loss of
a state of jiurity),
we may without
E and
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
60
and
for
i)=:0
Avith reference to
substance appears,
or, if
the substance
is
in
which the
states of its
components
^"and Zf cannot
in general
be treated as arbitrary.
We
= c^^ 'Em
cte f/f
:= an =m
^ ell]
a
V
civ CIV
/  cE + \e~Em, ,^rI
c+a
H
'/
m^ /
M
\
(tni,
(256)
^ '
t
p=ia
1.1=1
Em,
c
m
,
(257) ^
Em
cv
III
(25S)
^
'
^ E
e
\
E
c
s (c
rii^
m+
ii).
(259) ^
v,
We
may
//,
t,
and
from equations
and
(257).
Eliminating
t
^ //,
we have
= Em + c m
~
and
f.\ovt=
i/,
{
a log
and eliminating
?/'
we have
= Em
+m
H clog
obtain
t f
<i
log
'^
.
(260)
we
m H
I
\
c log "
+
{
a log
m/
cit
dv
V
^
Ie +
't
IT
log
t \
a log
jdm
(261)
212
J.
W. Gihhs
?7=
m (^+
clog^+alog j,
(262)
P = ,
c\aJIc\ogt^a\og
From
(260),
\.
(263)
(264)
by
(87)
\
and
i
(91),
we
obtain
c log
t
aT'?
'C,
= Em
mt
a log
+
I
^^ v,
(263),
we
= Em + m tic +
this,
H  (c+a) log
a log
j.
(265)
From
by
differentiation
(92),
we may
if
log
),
(266)
^s
v= amt
P
/^
(267)
E+
tie
\
H
((+ a) \og
a log
(268)
in
The
form
last is also a
fundamental equation.
It
may
be written
the
log
or, if
^=
a
e
+ ^^ a
c
t
log
t+'~,
at
(269) ^
we denote by
Hca
+a
.
fiE
e
p
easily obtained
;
=:
ae
(2<0)
/;,
j,
p, and
may
also
be
{c+a) ^
(271)
which can be solved with respect to j. Any one of the fundamental equations
and
(271),
./
W. Gihbs
213
Hca
a
in
e
"
and another
for
given
'
the above form, in order that the relations between the constants
The sum
c+a is the
we
difierentiate (266)
*
regarding^ and
as constant.*
We may
of a
saturated vapor,
we know
specific
may
and
by
V.
we
shall
liquid
d?/
k
t
dt,
whence
?/
= Alog
log
t
+ H',
equation and
(97),
a constant.
dfi
Also, from
tliis
(k
whence
/n
= ktM log
This
tH'
is
+ E',
(A)
constant.
stance in the gaseous state, the two equations will both hold true of coexistent liquid
and
gas.
Eliminatmg u we obtain
log
p = HH' + kca a a
is
k~ca
logi!
EE'
at
V
a
p
^.
t
If
we
we may
write
,
i)=AB\og
If
A, B, and
C denoting
constants.
state, the
we make
coexistent solid and gaseous phases will of course have the same form.
tent with
two
and density.
we may
log
= k'tk'l =
tHt+
E,
and
and
= E+t(c + a H
(c
+ a)
log
+a
log
j.
214
./.
W. Gihhs
Equillhrium of Heterogeneous
is
Substances.
of constant
entirely determined
/I
by a
single
Now
that
if
of the
first
quantity
+/
of the second
it
will
/":j+A//,
=(1
+>^)/I.2.
fi,,,
given above,
we
^=^
C log ^ )
^+
^,
when
^+^g' (l+^ A
g''caAfc' +
(l
+ X)A;^
B (l+?i)k"a Wca
E+lE'{\+l) E"
a
(1+A)F"AF'
a.
We may
may be
applied to
by
its
and
I)
must
in this case
be under
stood to denote quantities which vary with the composition of the liquid.
consider the case more in detail,
"^
But
to
we have
by
(a)
m
where
liquid.
k,
u=ktkt\os tH't+
Vp + E',
H'.
F,
E' denote quantities which depend only upon the composition of the
Hence,
we may
write
C
where
k,
H, V, and
the several
components of the
liquid).
Hence, by
^
,
(92),
//,
dU.
jt+ ,
dV
dmi
arw,
dE P+ a?n, T^
which
also forms the gas,
If the
.shall
component
to
which
we
have by (269)
log
p ^ =r a
Hca
a
+ a^
log
<
+ 'i
at
H\E
.
Eliminating
;"
,
i
we
log=^51og<^+ D^,
a
in
it
dk
\
I
which
A, B, C,
and
Z>
^ dU
dm^
1
dm
ca).
,
B=l' a dm
\
/f^k
\ /
J.
W. Gibbs
215
variable (m).
We may
It is a rule Avhich
many
cases very
sub
in the
gasmixture
equal to the
sum
same
Now
which
yields in the
liquid or solid
in
in
its
equilibrium with
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
i^
=('*)
(272)
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 others, but as it is well known that the above rule does not apply to cases in which sucli absorption takes place to any gi'eat extent, we
may
effect of this
which we have
do
is
of secondary importance.
we
neglect the
due
to these
circum
may
be expressed as follows
The pressure in a mixture of different gases is equal to the sum of 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 to contain in each of the descending end and bent in the form of a
the pressures
am
a dm.
With respect
to
some
of the equations
may compare
which have here been deduced, the reader Ueber die Spannung des Dampfes von Mischungen
civ. (185.^), p. 6] 2
;
"On
Saturated Vapors,"
Pliil.
Mag.,
vol. xxxi.
(1866), p. 199.
216
J.
W. Gibbs
loops one of the liquids, and above these liquids the gases which they
emit, viz., the separate gases at the ends of the tube,
We
may
Now
it is
in
same
level,
the form
sum of the
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.
surfaces
may
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 distinguish by subscript numerals the quantities relating to the different
and denote by ^\ the sum of all similar terms obtained by changing the subscript numerals, we shall have by (270)
gases,
I
a,
a,
t
,<
]
p=^,
\i
(273)
fundamental equation defining an ideal gasmixture, and afterwards to justify the suitableness of such a definition by the properties which
it.
In particular,
it
components remains constant, has all the properties which have already been assumed for an ideal gas of invariable composition it will also be desirable to consider more rigorously and more in detail the equilibrium of such a gasmixture with solids and liquids, with
;
By
differentiation
H,Cjaj
\
c,
fi^Ei
^1^
I,
V
f
J.
W. Gibhs
217
H9C9
V
etc.
HiEi
(275)
I'ehition
the density of any component, and the potential for that component,
They may
/^i
[
)
(276)
etc.
Eliminating
from
(2 73)
and
(276),
we
obtain
(277)
(278)
gasmixture
is
equal to the
if
sum of
From
(276)
tion between
1/:,
and (277) we may easily obtain the fundamental equat, v, m^, ni^, etc. For by substituting in (94) the
taken from these equations,
(
values of j(?,
ij)=
If
we
obtain
2J^^m^\ni^t
Cj ^iCilog
f
a^log
j).
(279)
this equation
as constant,
m
c
for
^1 ^1,
for
(c,
m,),
am,
for
for
Em
and
Hm,  a m
of
c,
losf /n
for
^1 {H^ ni^a^ mj
log m,^).
The values
a,
E, and H,
will
m will
denote
As
III.
April. 1876.
218
J.
W.
(xibhs
form of
(260),
it is
components remains unwe have assumed for an The relations composition. between the specific invariable of ideal gas volume constant and at at constant pressure gasmixture of the heats components are expressed by the equations its of heats specific and the
(273) or (279),
when
changed, will
have
all
e=^^'^\ ni
and
c'
(280)
+ a=^\''^^^l^^i.
(281;
have already seen that the values of t, v, m^, /.i^ in a gasr mixture are such as are possible for the component G^ (to which
We
m, and
j, Xi,
/<
Cj
If we denote by p^, //j, ?/'j, several quantities which the connected values of the the
relate) existing separately.
letters
indicate
rately,
and extend
we
shall
have by
(273), (274),
and (279)
P=^iPi,
whence by
(87), (89),
'/=^i'U,
and (91)
t=^i'l\\
l^^',;,.
(282)
f=^'ifn
The
quantities p,
>/,
A'=^'iJi,
//,
(283)
f,
j,
'C,
may
be attrib
uted to the several components in such a mannei 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
that
if
It is in this sense that we component existed separately. should understand the law of Dalton, that every gas is as a vacuum
to be
sible for a
without any limitation in regard to the thermodynamic properties of They are all consequences of the law that the
pressure in a mixture of different gases
is
equal to the
sum
of the
by
itself at
the same
For let temperature and with the same value of its potential. relating to the be defined as etc.; etc. P2i Pii V\i ^1^ 'I'l^ Xn ^1
l
different
by
itself
perature,
and potential
as in the gasmixture
if
= ^iPi,
J.
W. Gibhs
219
and
tlierefore,
by
in the
gasmixture, and in the separate gas to which p^, the same and may be denoted by the same symbol
etc.
relate, is
nt
^.
Also
dt
j/^i,
f^"
'\ dtj/i,
"
whence
also,
by (93)(06),
All the same relations will also hold true whenever the value of
for the gasmixture
is
//
equal to the
sum
component
in
For
'/';,,
Xn
?i
P2'>
etc.
by themselves, we
whence
have
/dif^\
Therefore,
=(&1l\
by
mixture and
over,
in the
gas
6r,
More
\dt
/ij^ ffi
dt
/v,
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.
when the
*
initial
subscript
in this
m.^, etc.,
unless
its
is
applied, is to
be regarded as constant
220
tT.
W. Gihbs
are the same, (whether these gasmasses are entirely difterent gases,
is
If
we
is
in equilibrium,
two
different points
and denote the densities of one of its components at by y and ;//, we shall have by (275) and (234)
^
^^,
^''
e
=e
*''
.
(284)
From
which we may regard the quantities distinguished by accents as constant, it appears that the relation between the density of any one of the components and the height is not
this equation, in
aflfected
by the presence of the other components. The work obtained or expended in any reversible
process of com
when
used are
all
the same,
ip
final gasmasses.
equal
to the
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.*
of the quantities of
sum
We
will
now
which
it
may
is
may
first
when the
liquid
is
pro
way from
This
may be
*This
It
by Lord Eayleigh,
will
assumed
J.
W. Gihhs
221
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
substance which
it
and
there
same substance
in the
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
is
necessarily the
common component
and the temperature
remain unchanged.
the potential for S^
we denote
by dp and
\d2)jt,m
<?/<,,
we
shall
have by (272)
\dmjt,p,m
it is
the index
(l)
affixed refer
to the liquid.
as if the
at the
(^(
d
;
log
/>j.
Therefore
(dv
This
dp. dmjt,p,m ^I
\^^^
(285)
^
may
be integrated at once
if
we regard
which
the differential
coeffi
member
as constant,
approximation.
so accurate, if
We may
we
vrrite the
(dv
where
j/^
>S^
in the gas,
and
dv Y^^
p,
ipp')
where p^' and p' denote the values of p^ and component of the gas is entirely wanting. It
p when
the insoluble
pp'
is
relates.
is
not neces
222
J.
W. Gibbs
Equilibriu
in
of Heterogeneous Substances.
of the gas and liquid.
If there
common component
are others,
we may
effect of a
gas which
is
absorbed to some
in strictness
ponent of the
liquid
We
may commence by
previous,
formed of the same components. Using a notation we shall have by (98) for constant temperature,
like the
and
d})
;/\^^ d^i^^y'i'^
d^i^
whence
{yf^Yx)
<^Ml
=
^
(/2H'^O
^/'2
Now
if
is
an ideal gasmixture,
dp,
^^
d^' u
therefore
=z
^ ^ dp ,=.
and
,
//
dp ^ , = = a^t
,
^^,
P,
r.
P2
dp^.
72
^
We
liquid,
\\dp^=\\^\
/S',
(288)
may now
and
S.^ is
suppose that
a gas which
it is
is
is
extent.
In such cases
well
known
of the substance S2 in the liquid and in the gas is for a given temperature approximately constant. If we denote this constant by ^,
we
shall
have
lU
It
Udp^={\ A)
this
/>j
is
dp,.
;/j
(28P)
as variable,
equation regarding
we
accuracy
if
we regard y^
as well as y^
as con
We
('l)(Pt^i')=(l^l)
P2^
('^90)
where ^j' denotes the pressure of the saturated vapor of the pure It will be observed that when .4= 1, the liquid consisting of S^.
presence of the gas
/S'g
gas S^.
When
if
greater than
yl<l, the pressure and density of the gas S^ are S.^ were absent, and when .i>l, the reverse is true.
J.
223
The
properties of
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
little less
than the
sum of the
it
pressure of the
make
little
more, when
would appear that in this respect our formula? 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
this circumstance.
It will also be observed that the statement of Dalton's law Avhich we have adopted, while it serves to complete the theory of gasmixtures
is
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 ditierent gas which is not absorbed
by the
in
solid or liquid, if construed strictly, will involve consequences regard to solids and liquids which are entirely inadmissible. To
this,
assume the correctness of the rule mentioned. Let of the gaseous and liquid or solid masses, and S2 the insoluble gas, and let quantities relating to the gaseous mass be distinguished when necessary by the index (g), and
show
aSj
we
will
denote the
common component
by the index
(l).
gas
it
is
in equilibrium
solid, let
its volume and the contains of the other component, as well as the temperature, remaining constant. The potential for S^ in the oaseous
quantity which
mass
increment
\dmj
and the pressure
/
dm 2
t,
V.
increment
dp\^^^
V,
\dm2lt,
^'
Now
and
/:>.
But by
(272)
dp/t,m
\dmjt,p,m'
224
T.
IV.
Gibhs
Therefore,
dm 2
ft, V,
dp yG)
Xdm^Jt,
It
V,
m
of this equation relates
will
first
member
gas.
Now
and the second member solely to the we may suppose the same gaseous mass to be capable of
first
memsuch
ber of this equation must therefore have the same value for
liquids or solids
;
all
which
is
quite inadmissible.
is
solid
identical in
which
gas
it
Hence, Avhen a
in the solid
its
components both
is
and liquid
water),
it
when
a moist gas
in equilibrium
solid
the same
The foregoing
we have
chosen.
It is of course
immaterial whether
(273), or
by
(279), or
we regard the definition as expressed by equation by any other fundamental equation which can
for an ideal gasmixture corresponding
and (271)
may
easily
They
are
=7+
};
^\ (. ,
log^.^^^
 ^,)
j
^,..,),
(292)
= 2jB,m^+
 ^\
(c,
m, (c,+,
m,)
t
m,
+ a,
log
+^\
(a,
m,
log
^^^^^).
(293)
The components
may (291) (292), 293) refer, may themselves be gasmixtures. binary gasmixture equations of a fundamental the apply for example
We
J.
W. Gibbs
225
hydrogen and air, or to any ternary gasmixture in which the proportion of two of the components is fixed. In fact, the form of equation (279) which applies to a gasmixture of any particular number of components may easily be reduced, when the propor tions of some of these components are fixed, to the form which applies
to a mixture of to a gasmixture of a smaller
number of components.
to the gases of
components must be entirely diiferent from one another with respect which they are formed by mixture. We cannot, for example, apply equation (279) to a gasmixture in which the components are oxygen and
air.
It
Such an equation might be derived from (279) by the proper substitutions. Hut 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
equations which have been given,
ent from
its
is
all
the
components.
is
vapor of water
ties of the
having the
quanti
This
of
its
is
certainly true
when the
components are all independently variable in the gasmixture, without change of temperature or presCases in which these quantities are not thus independently sure.
variable will be considered hereafter.
and
Solids.
Such equations
as
(264),
(268),
(276),
potentials in pure or
not confined
common
to coexistent liquid
and gas
eous masses have the same values in each, these expressions will generally afford the means of determining for liquids, at least approximately, the potential for any independently variable component which
is
For although
not such as can exist in contact with a will always be possible, when any of the components
volatile,
are
to
bring
it
by a
change of pressure
temperature and
is
May,
1,s7<;.
226
J.
W. Glhbs
volatile
may be
The
pressure
in
trifling
as
composition, and
may moreover be
The same
readily estimated
by means
of
equation (272).
of the
As an
application of
let
this
in liquids,
absorption of
make gases by
us
in
the
ni^l'^
/<
j
the the
common
and
liquid, v^^^
and
When
we have by Henry's
law
,y(L) (L)
' '^
,,(G)' y
^^
and by (76)
'
where
^1 is
I<,
J^+ (Mog^,
ni
(G)
(295)
jB
and
Therefore
(296)
A.,
It will
be seen
is
(if
we
equation
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
by the
pressure,
we might
anticipate
that these quantities in the case of liquids might be regarded as functions of the temperature alone.
./ TV.
Gihhs
227
111
(218),
that by (204) and (276) they are shown to liold true in ideal gases or
gasmixtures, not only for components which form only a small
of the whole gasmixture, but without any such limitation, and not
It is noticeable
and (J are functions of the tjmperature 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
sufficiently rarefied,
when
we may regard
is
sufficiently
When
question
and
C may
not be
mass
also
components.
These equations
will
components of Avhich the density in the licjuid 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
apply, as
seen, to the potentials in liquid bodies for
we have just
to
the
From
equation (278)
we
may
easily calculate
the increase
ai'e
of
mixed by
Let us suppose
that the quantities of the gases are such that each occupies initially
we denote
m,^ j log
(f^)
this
volume by
T^,
the
m^
a 2 log
{ni
^
T^
V
z
w/g ^2 ^^g"
~?
z
or
XT JSlow
(/j 1
m^
log
2.
m,11 a.
=z
P^

1 and
2t
m^ ^
a,
^
P^ =~ It
(297)
may
2.
pV . log
It is noticeal)le that the
228
J.
W. Gihbs
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 tlie following considerations. When we say that when two different gases mix by diffusion, as we have supposed, tlie energy of the whole remains constant, and
of diflferent kinds.
we mean
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 ceitain amount of heat from a warmer
But when we say that when two gasmasses of the same kind are mixed under similar circumstances 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
to a colder body.
is
entirely impossible.
We
call
as
when they were unmixed, because we do not recognize any difference So when gases of different kinds in the substance of the two masses. 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
tion as at
shall occupy more or less exactly the same posisome previous epoch, but only a state which shall be undistinguishable from the previous one in its sensible properties.
It is to states of
of thermodynamics relate.
But
if
why
is
we have supposed,
is
Now we may
are embodied in our eqixations 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 betAveen 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 We might of the degree of similarity or dissimilarity between them. should be absolutely of two gases which the case identialso imagine (sensible and molecular) which properties come all the into cal in gases either pure or mixed with each exist as while they other, play
J.
TT\
Glhhs
229
differ in respect to tlie attractions between their atoms and the atoms of some other substances, and therefore in tlieir tendency to combine witli sucli substances. In tlie mixture of such gases by diffusion an increase of entropy wovdd take ))hice, although
any
in virtue of their
tlie
geneous gas into the same two parts into Avhicli it has once been divided, after these have once been mixed. In other words, the
impossibility of an uncompensated
reduced to improbability.
There
is
perhaps no fact
in 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
established as that the
quantity 
pV in
Z
(2f7)
And
is
therefore
independent of
The
result is of the
ai'e
we denote by
volumes of the
of gas, and by
V as
increase of entropy
may be
Vwe
r,
2^ (m,
a^
loguj.
And
if
we denote by
r^
shall
=
:
Cm^
,,
Cm^
: :
a^,
etc.,
where
denotes a constant.
V
J
Hence
r,
:
V: '.m^a^: 2^{ni^ay)
^',
?,
may be
written
(r,
2,r^\og2,r,  ^\
log r,)
^
230
J.
TK Gihhs
The Phases of Dissipated Energy of an Ideal Gasmixture (Joni2yo7ients which are Chemically Related.
We
will
now
page 200) of an ideal gasmixtiare, in which the nnmber of the proximate components exceeds that of the ultimate. Let us first suppose that an ideal gasmixture has for proximate
energy
(see
components the gases G ^, G^, and G^, the units of which are denoted by @^, (S).^, 3, and that in ultimate analysis
@3
A
J
= A, ,
+A22,
(299)
Ag
1.
The
phases which we are to consider are those for which the energy of
the gasmixture
a
minimum
(86),
yUj 6rti^
4 /'o
f^""'o
Ms
^'it^^O.
(300)
G^ and G^ as determined in ultimate analysis. Values of 6tn^, Sm^, Sni^ proportional to A,, Ag, 1, and oidy such, are evidently
therefore
Ag
//2
= Ms
(301)
we substitute in this equation values of /.i^, /<2, Ms taken from (276), we obtain, after arranging the terms and dividing by t,
^1 i log
"^+ ^2 2
log
~'^
^'
1
(>s
log
'^
= A^B\ogtj,
1
(302)
where
A=\^H^ + ^2^2 ^3 
 ^^2^2 + ^3  ^
f Ag Cg
 ^ 32 + 35
^ = A,r,
If
C3,
^3.
the gases
ard conditions of temperature and pressure) of the quantities of 6^j and G^ which are contained in a unit of volume of the
gas
6^3,
we
shall
have
/i,
= ^\
and
/:/,
=r
^,
logi5
.
(306)
and (302)
will
log
'
,3
^=r
_i_
(30/)
J.
W. Gibhs
231
Moreover, as by (277)
pv
12
m^
+ a^ m^)
t,
(308)
we have on eliminating
W
;/t3
^1
[a I
"'2
m, H
m^
+ 3 Wg)
= ^ + ^^^^'.71'
O
'f'o
tC o
('*'')
t'
where
B'=X^
It will
C1
+ A3C2
 <'3HAii
Agtt^
3.
(310)
be observed that the quantities /S^j, /^g will always be positive and have a simple relation to unity, and that the value of /?j + /^2 * 1 will be positive or zero, according as gas 6^3 is formed
of Gj and
G^ with
or without condensation.
If
we should assume,
according to the rule often given for the specific heat of compound
gases, that the thermal capacity at constant
of the gas
6^3
is
it
equal to the
quantities which
would be
zero.
Gq
and
6^35
by
(283)
and (257)
A,
(^c,t
+ A\)\X2
satisfied.
(cot
+ B.J
(c^t
E^),
or
which
Avill
reduce to
is
specific heats
evolved divided by a^
the second
member
Moreover,
the heat evolved in the formation of a unit of the gas G.^ out of the
G2 imder
t
constant pressui'e
1
is
which
It
is
4 0\ A
a,
I
a^tB't\ C,
member
of
t'^
multiplied
by
m^^
a,^
in
the case
tn^,
when
y6^j
/ig
for
any given
values of
;;/j,
and
(infinitesimal values
infinite), it will always be possible to assign such a finite value to v that the mixture shall be in a state of Thus, if we regard a mixture of hydrogen, oxydissipated energy.
gen, and vapor of water as an ideal gasmixture, for a mixture containing any given quantities of these three gases at any given tern
232
J.
W. Gibbs
EqiiUihrium
of Heterogeneous Substances.
be a certain volume at which the mixture will be In such a state no such phenomenon
of platinum.
(If
water into
its
components.)
It
may
temperatures, except
when
is
oxygen
entirely
is
of dissipated energy
lie
It is also to
so unfavorable to
any
may
short of
what
is
But with
which we should suppose that the laws of would apply most perfectly. But when the compound gas G^ is formed of G^ and G^ without condensation, (i. e,, when /?, + /io 1,) it appears from equation (307) and between m^, m^, relation /^g which is necessary for a that the by the temperature alone. determined energy is phase of dissipated quantities of the gases G^ and total if regard the we In any case, of the gasmixture), and G2 (as determined by the ultimate analysis of these gases which also the volume, as constant, the quantities
tion are precisely those to
ideal gasmixtures
appear uncombined in a phase of dissipated energy will increase with the temperature, if the formation of the compound G^ without
change of volume is attended with evolution of heat. Also, if we regard the total quantities of the gases G^ and G^, and also the pressure, 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 G^ under constant
pressure
is
If
^=
0,
(a case, as
has been seen, of especial importance), the heat obtained by the formation of a unit of G^ out of G^ andtrg without change of volume
or of temperature will be equal to
G.
If this
quantity
is
positive,
and the
(for a
G^ and G2 and
also the
t
volume
have
have given
an infinitesimal value of
we
shall
phase of dissipated energy) an infinitesimal value either of mj or of 25 '^'^"^ ^^^'" ^" iiifiiiite value of t we shall have finite (neither inBut if we sui)pose finitesimal nor infinite) values of m,, mg, and m^.
the pressure instead of the \'olume to liave a given finite value
(with
J.
W. Gibbs
233
values of
is
The
ture,
fact,
case which
we have considered
is
may
easily
be generalized
this respect.
In
in a gasmixture, if
may
form
A,
@,
+ A2o +
A3
@3
etc.
0,
(311)
where @i, 2? ^^c. denote the units of the various component gases, and A,, Ag, etc. denote positive or negative constants such that
^\
A,
0.
From
A,
we may
sipated energy,
/<,
f
Ag
^lo
A3
/<3
+
0.
etc.
0,
or
:^\.(A, /^)
(312)
Hence, by (276),
^^(A.ilog'^) = ^ +B\ogt~
where A,
,
(313)
B and
(J
by the equations
(314)
4
= 2,
B=z^,{\,c,\ G=2,{X,E,).
Also, since
j)
(315)
(316)
(a
,
v =^
nt
t, ^ )
^1
(A, i
logw,)
 2
(A^ a,)
,
log^\
(a,
m,)
(317)
H ^^ (A
,) log
p = A\B'\ogt,
where
(318)
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
simultaneously for phases of dissipated energy.
It will
ti'ue
dis
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
III.
May,
1876.
234
J.
W. Gibhs
From
follows that
if
there
is
a phase
The equations
mixtuie, the
com
same
potential,
and
if
we
write
/i
for
log
m/
i
_A _
d
_^
.'
B _ lop2 ^
;;
(J
m^
131
<(2 f
where
J.
W. Gihhs
Eqiiilibriuut, of Heterof/eneous
Sv^hstance^.
235
In the first place, if we consider the case of a gasmixture which only differs from an ordinary ideal gasmixture for which some of
the
in
in
that there
is
perfect freedom
it
follows at
brium
is
we have
been deduced
Tf
it
in
we
might still suppose the particular phases which alone can exist to be determined by some other j)rinciple 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 temperatui'e 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 gasmixture are the
same as
for
an ordinary ideal gasmixture, in which the components are not convertible. Let us denote the quantities of the n' proximate components of a gasmixture
by m^, m^,
etc.
etc.,
its
n
v,
{n denoting a
and
let
entirely determined
6, 7,
by
v, t,p.
may evidently imagine such an ideal gasmixture J^ having n' components (not convertible), that every phase of ^ shall correspond with one of J^ in the values of e, 7], v, t,p, m j m^, etc. Now let us give
,
We
to the quantities
mj,
1112, etc. in
the gasmixture
let
and for the body thus defined page 1 74) constructed likewise
;
us imagine the
surface (see
let
us
imagine the vr/s surface constructed for every set of values of m^, ^2, etc. which is consistent with the given values of m,, m^,
etc.,
i.
e.,
for every
body
would be
in2
etc.
It follows
immediately
from our supposition, that every point in the vrjs surface relating to A must coincide with some point of one of the vt/e surfaces relating
236
to
./.
W. Glbbs
Jqullibrmiii.
of Heterogeneous Substances.
B not only in
must be tangent to the various yr/ surfaces relating to B, and therefore must be an envelop of these surfaces. P'rom this it follows that the points which represent phases common to both gasmixtures must represent the phases of dissipated euergy of the gasmixture B.
surface relating to ^1
The
properties of
are
assumed
in
demonstration are expressed by equations (277) and (278) with the equation
f
= ^,
(c,
;//j
4
/// ,
E^).
(324)
It is usual to
assume
in
components that the convertibility of the components does not affect 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 gasmixture the compothe relations (277) and (324).
ponents,
(i. e.,
if
can
take place
among
will
be
sufficient to
assume, in
equation (277) and of the following, which can be derived from (324)
by
differentiation,
and comparison
a necessary relation,
[tdtji^dv 
:^^ (Cj
m^)dt\,
= 0*
It will
if
(325)
We
shall confine
be observed
is
that
the gasmixture
culated
tible.
proximate composition, the heat absorbed or yielded may be calby the same formula as if the components were not conver
Let us suppose the thermodynamic state of a gaseous mass J/, of such a kind as has just been described, to be varied while within the (The quanlimits within which the components are not convertible.
tities of
ulti
* This notation
etc. are
regarded as constant
J.
TT''.
287
mate,
trical
ai"e
supposed constant).
we use
the same
method of geomevqB
and position of
sition of
M.
composition.
It is
occur
when
the limit
is
is
composition
convertible
uniform.
formed by phases in Avhich the proximate The line traced in the region of convertibility
Drfs.
continued beyond the limit of components of ill/, 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 vr]s. surface of the body J/, which is here a gasmixture of converas
same component?
before,
tible
components.
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 w// surface of the body in the region of convertibility must thus be
surfaces
tangent to
tion of
all
in
which
be capable of experimental demonstration, the former surface must be an envelop of the latter surfaces,
may
and therefore a continuation of the surface of the phases of dissipated energy in the region of inconvertibility.
laws of ideal
vertible.
It
a measure oi a priori probwhich are obtained by applying the ordinary gasmixtui'es to cases in which the components are conis only by experiments upon gases in phases in which
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 equaThat this substance in the gaseous state tions to a very critical test.
their
is
density
238
J.
W. Gibhs
Eqii'dlhriiuu
of Heterogeneous
l^ubstances.
NO2
N^O^
is
from the depth of the color on the supposition that th^ absorption of
light is
due to one of the components alone, and is proportioned to the separate density of that component.* MM. SainteClaire Deville and Troostf have given a series of determinations of what
we
We
usual in treatises on
viz.,
or
more
strictly,
an ideal gas which has the same density as air at the zero of the
In order to
by these determinations,
it
will
be convenient to
transform equation (320), so as to give directly the relation between the relative density, the pressure, and the temperatiire.
As
pressure
may by
(263) be expressed
by
tiie
formula
the relative
may
be expressed by
(326)
I>=
(m, imo)'^.
Now
by
(263)
pV
By
tions,
= = 2J\,
1^2
= ,
D
(328)
when the gas consists where D^ and D2 denote the values of wholly of one or of the other component. If we assume that
JJ.,
(329)
we
shall
have
,=:22
(330)
From
(326)
we have
'
J'
vol. Ixvii, p. 488.
*Salet,
f
"Sur
la coloration
Comptes Rendus,
J.
^^vbstances.
239
and from
by
2
(328)
and
hi.,
(330),
m,
= Z>o ^ 2 i5, ^
i>)^^,
(331)
whence
m.
= (i>,
m, By
(327), (331),
= 2(i>/J.)^^.
log
(332)
log
*=
= 2 ^^ 2 (Z)  Z> J
r.\
^
'^
(333)
if
a,
we
introduce
common
logarithms (denoted
by
log,^)
instead
t,,
of
instead
instead of
2^
the pressure in
a, to
'""%i~Jj = ^ + I S."
where
nected with those of
+^)
 M^3
('^'^
A and C denote constants, the values of which are closely con^ and C
64 ^ = 28 + = 1.589, and B^ .0691 = 3.178. 2
^
'
From the molecular formuUie of peroxide of nitrogen N0 and NoO^, we may calculate the relative densities
D,
14 4. 32
=z
2
.0691
(335)
^
The determinations
of
MM.
2>)2 ,
,^
3118.6
which gives
i>=:3.l78
(>
\/<'^
(3.178+0)
where
In the
first
log^^
W= 9.4/056
 fTr^~^^Si oPa,
3118.6
umns
ments of
from these
Deville and Troost, the relative densities calculated numbers by equation (336), the relative densities as observed, and the difierence of the observed and calculated relative
MM.
240
J.
W. Gibhs
It will
Equilibrium
of Heterogeneous Substances.
densities.
in
no case reaching
be observed that these differences are quite small, .03, and on the average scarcely exceeding .01.
The signific.^ance of such correspondence in favor 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 pressui'es than
that for which the constants have been determined, such correspon
t,.
J.
W. Gibhs
241
peroxide of nitrogen by
and (336)
will not
be attected
by the presence of free nitrogen, if the pressure expressed by p or /> and contained implicitly in the symbol IJ (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
the pressure due to the free nitrogen from the total pressure.
We
may
in the
reduction
by which the numbers in the column of observed were obtained. Besides the relative densities calculated by equation (336) for the temperatures and (reduced)
of the observations
relative
same temperatures and the pressure of one atmossecond and third experiments
The reader
the
Wanklyn
and
there
is
between
observed values of
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.
first
and
also
fourth observations
We
must
by
as
equation (336) for the temperature of the experiment and the pressure of one atmosphere.
established
directly
Now
the
number
1.687
we may regard
by the
experiments of Deville
and Troost.
less
For
in seven
we accept
by by experiment,
than
.01.
the effect of
As
this result is entirely at variance with the facts observed in the case
the three
other determinations
of Playfair
and
Wanklyn,
May,
187(5.
242
J.
W. Glbbs
observation.
The
experiment of this
series
cannot thei'efore
Similar considerations
experiment.
last
By
compar
experiments
may
easily convince
we admit
first
two
the series, which have the greatest weight), the last determination of
relative density 2.588
must be too
small.
In
fact, it
should evidently
we
as
good
as could
be desired.
Nor
will
the admission of errors of .152 and .120 (certainly not large in deter
first and fourth experiments involve any serious doubt of the substantial accuracy of the second and third, when the diflerence 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
not
In
the experiments
of Deville
and Troost
the gas was subject to the actual atmospheric pressure at the time of the experiment.
The
not given.
In the ex
Wauklyn
The numbers
in the
column of
pres
sures express the fraction of the whole pressure which remains after
But no indication
is
given
in the
Now
p
it
may
easily
be shown that a
vai'ia
in the value of
In any as calculated by equation (336). than .005 in the value of Wanklyn variation of more of Playfair and a experiments the of
than 30""" 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 thei'efore 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
densitv, as the reciprocal of the latter quantity
is
J.
W. Gibhs
243
periment of this
sacrifice of
series.
seemed
best, however, to
make
a trifling
It might be thouglit that the experiments under discussion would be better represented by a formula in which the term containing log t But an examination of the figures (see equation (333)) w^as retained. in the table will
in
this
respect,
and there
Any
equation (333), (assuming the absolute validity of such an equation for peroxide of nitrogen,) from the ex,
values of ^, B'
and
in
may easily convince himself. From equation (336), however, the deduced. By comparison with (334) we
reader
^
,
following conclusions
obtain 3118.6
may
which must hold true approximately between the temperatures 11*^ and 90*^'. (At higher temperatures the relative densities vary too
slowly with the temperatures to afford a critical test of the accuracy
of this relation.)
By
dift'erentiation
we
obtain
J/:S'C_ 3118.6
where Jf denotes the modulus of the common system of logarithms. Now by comparing equations (333) and (334) we see that
^= C
Hence
B'
which
t\
MC =.43429 C
rtj,
40*^^
G 7181 2 = 3590
G
may
or
50*^,
and
mentioned.
Now
B'
t \
by the conSuch
version of a unit of
NO2
into
NgO^
But
since
by equations
(322)
B'
B\a^
= ^ + ii,
a,.
we
shall
40^^^
Now
t \
when
a unit of
NOg
is
transformed into
NgO^
It therefore
244
J.
W. Glbbs
external forces
when
NOg
if
J5zii 0,
^^'^
e., if
NO^
and
^2^4
^^
same.
This assumption
would be more
B' :=
0.
If JB
0,
H'
= u^.
Z>,
If
we
t,
p, and
we may
substitute
6.5228
for the second
log,
(C
+ 2V3) ^ j^^^Tf:^'
2977 4
calculated
member of equation (336). The relative densities by the equation thus modified from the temperatures and
any
case, or
by more than
It is to
be noticed that
relation expressed
we by equation
if
which
is
evidently equivalent
to an equation between p, t, v, an<l ni (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
is
sufliciently rarefied to
be regarded as con
wholly of
we must also admit the same limits of temperature and density) of all the calorimetrical relations which belong to ideal gasmixtures with The premises are evidently equivalent to convertible components. that we may imagine an ideal gas with convertible components this, 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
approximates to
limiting value 2>,,
validity (within the
a very ^reat value of v (within the given limits of temperature) the thermal capacity at constant volume of the ideal and actual gases Let us regard t and v as independent variables shall be the same.
but
and
real gases,
entropy
//'
Now
by
(88)
./
W. Gihbs
245
= *,
dr]
(387)
therefore
d
do
dij
7lt
_ d ~ lit
d_
dv
_ ~
d dp
dt
?/',
_ ~di ~
we
drp
~dt^'
'
ns8^ ^
obtain
dj}^_d_
dt
dr[
dt''
dv
dv
which must hold true within the given limits of temperature and
density.
Now
it is
granted that
^'#'
dt
for very great values of v at
(for the
(3^0)
^
'
dt
limits,
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
?/',
w^e shall
dt}
have
dt}'
dv
dv'
is
v
all
From
it
evident that in
calorimetrical
and
we
may
given values of
relation
and
v.
Hence the entropies of the two gases are and on account of the necessary
;
de=.
dr]
p dv,
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
phases of equilibrium.
the use the equations of the form (312) to eliminate from the equation of the form (273)
For
this purpose,
we may
which expresses the relation between the pressure, the terapeiature and the potentials for the proximate components, as many of the potentials as there are equations of the former kind, leaving the
246
'/
W. Gihhs
is
convenient to regard as
may be denoted
by
//,
will
be
C2\a.2
fi
',
\a.^Lt
Ei
,
p:=za^L^t
where
(342)
L,
""'
X.^e
"^
(343)
(98),
From
obtain
this equation,
by
differentiation
we
nE,
e
^2(^2
Ci
+2f"
fi
^5
',
(244)
E,
\
Ci
IIE^
e
^
.
=L^t'e
From
following
is
L^t
(345)
II Ey
"'^
Cj_
iiEj
""'*
 = Z^{c,t+E^)t'''
We
//
+L^{e2t+E.^)t'''
t,
(346)
may
v,
and
by eliminating
as follows
from (342) and (345). For this purpose we From (342) and (345) we obtain
may proceed
pa,t'^={a,a,)L^t
rtl
"'
"'^
(347)
li^Ei
a,.,t
,
'>
C2
+ az
rt,
a^t
(i ,
a^)
^2
"
(=^48)
^) "
2 log
^^
'^*
" ^^
)
= (^1 ~
^^s)
^^S (^ 1
pi
2)
^^^^^
jp
4
a^
~''2)log
~T^
'
J. IV.
Gihhs
247
=2 Wg
lent to (833)).
(346).
By
will
(347)
easily eliminate
fx
from
The reader
fundamental equation (34 2) 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 gasmixture
with com
in
that the equations derived from (342) do not give the quantities of
any
The practical application of these equations is rendei'ed more simple by the fact that the ratio , .a^ will always bear a simple I'elation to unity. When a^ and f/g are equal, if we write a for their common value, we shall have by (342) and (345)
j)V=zamt.^
and by (345) and (346)
(350)
m
By
_ L,{c^t+E^)^Lo{c^
JI
t\
E^)t
""
""^
CjCi El Eft at a
(351)
this equation we may calculate diiectly the amount of heat required to raise a given quantity of the gas from one given tempera
The equation shows that the 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
amount of heat
will
values of J, as defined by equation (89), for the initial and final states of the gas. From (89), (350), and (351) we obtain
C2C;
E1E2
e
''^
L,{c^t^ at^E^)^L^(c^t^at^E^)t
"
._^.
L^^^LJ,
By
differentiation of the
two
last
equations
we may
obtain directly
the specific heats of the gas at constant volume and at constant pres.
sure.
between
its
components
is
248
J.
Substances.
p = a^
,
di
a, e
a.t
0.2
cb.,
a.,t
+
where A^ and
X.^
'
'
^
,
(35.3)
Iiave the
230.
ERRATA.
Page
"
1G7, formula (168), for
m, read
to,,
. .
^,.
to_j read//,,
//_!.
Page
^.
a,t
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
consider
its
solid, it is
necessary to
state
of
strain.
A
is
body
is
said to be strained
when the
\^
altered,
and
of strain
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
cc', 2/', s'
any completely determined state of strain, which we shall call the state of reference^ and cc, y, z, the rectangular coordinates of the same point of the body in the state in which its properties are the
in
body
subject of discussion,
we may regard
;, _y,
z as functions of
a;',
y\
z'
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' ielate, as the strained and the 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 ic, y, z and x', y\ z', and do not imply any particular physical properties in either of the two states, nor prevent their
;
possible coincidence.
x'^
The axes
a*,
y,
2,
and
y\
z'
e.,
capable of superposition.
The
x\
;y',
state of strain of
and
z'\
y,
2,
when the
differential
coefficients
44
May,
187T,
344
./.
IV.
Gibhs
body.
When the diiFereutial coefficients of the first order do not vary sensibly except for distances greater than the radins of sensible
actioji,
molecular
we
niaj^
state of strain of
coefficients, viz.,
any element.
differential
dx
dx'^
^2/
dx
dif dy
dy'^
dx
dz'"'
dy
dz'^
^"
^^^^^
W
It will
dz
dz
dz
Ih''
%"
its
capable of
independent variations,
considered
six indepen
which do not
must be capable of
The
is
produced by
for the
in
addition or subtraction of
we
write
its
volume
the
we
shall
have
for
any constant
state of strain
But
if
we may
consider
6v
as a function of
7/v,
and
may
write
8e^,=.t
6,/y,
+A\. S^. +
CCOC
Av,
(^^
tv(j
+ A',, rJ^
(Jjt<j
_
dz
dz
^,
.^
dz
dz
fv
dx
where
A'x,,
.
.
dy
Zy,
d'T^
taken
witli respect to
y^,
j,
The
if
physical
signiffeation
of these
we apply
which in the state of reference is a right parallelopiped 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
J. TF.
Gibbs
Eqidlibrium
of Heterogeneous
Suhstanceti.
345
by
= A'x,
(^77,
dx' dy'
dz'.
Now
the
first
member
work
the second
member must
same value.
Since
we must regard
equal and opposite, the whole work done will be zero except for the
face
which moves
})arallel to
X.
And
since 3^,
<^'^'
dx
represents
the
distance
moved by
com
In general,
by the positive side of a surface for which x! is constant we understand the side on which x has the greater value, we may say that A"x, denotes the component parallel to A^ of the force exerted by
the matter on the positive side of a surface for which
a;'
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
Z', respectively.
X',
V,
With
this
understanding
we may
Sey.
t tf;/v<
:^
This
is
a given element
we multiply by dx' dy' dz', and take the integral for 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 incieased or diminished in substance
of the solid.
at its surface (the increment being
continuous
it
in
is
we must add
fey,
in
SX' Ds'
which Ds' denotes an element of the surface measured in the state of reference, and (^X' the change in position of this surface (due to the substance added or taken away) measured normally and out
ward
variation
of the intrinsic
therefore
346
J.
W. Oibhs
EquUihriuni of Heterogeneous
Suhstances.
y;
This
is
entirely independent
solid.
of
any supposition
in
regard to the
homogeneity of the
in contact,
of equilibrinni for solid and fluid masses the variation of the enei'gy of the whole
But
since
conditions of equilibrium for the interior of a solid mass and for the
surfaces
where
it
For
this it will
be
of the fluids
only
We may suppose
it
much
of the fluid as
is
in
is
close proximity to
which
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 sui'faces which can be generated
by moving normals
to the
may be
equilibrium of the
fluids.
It will
be observed
tliat this
method
is
is
entirely
enclosed in a solid.
necessary to separate the great mass of the fluid from the small
portion adjacent to the solid, which alone Ave have to consider.
Now
energy of the
fluid
mass
/' ,
will be,
by equation
(358)
f^t SDt]
 f^^p
dIJv
2^,r
^>'^'>*i
where f^ denotes an integration extending over all the elements of the fluid (within the envelop), and ^\ denotes a summation with regard to those independently variable components of the fluid of
which the
of the
If
solid
is
composed.
Where
term
is
of course to be cancelled.
we wish
we may suppose
of Z.
It is
that
it
acts
variation of the energy due to gravity for the whole mass considered
is
simply
(359)
where g denotes the force of gravity, and F' the density of the
J.
W. G/M/s
E<p',)UI)rliiiii
of
TIeterorjeneous Suhstdncei^.
347
We have,
ffft
Ds'
+fH dBtj
^p'p 6Dv
to
H :S , f'li^
Dm
^ 0.
(:H)())
{fVs,
^N' Ds'
+ J'^dDrj =
SDv
for
(3H 1
how
the value of
any element of
the fluid
solid,
dDv
where
a,
/i,
= {a
y body
(h
/i
6y
(^z)
Ds
;,
(362)
surface of the
which
y, z relate,
the element
state of
tlie
and
by
for
volume
(3)
how
the values of
dDni^, dDtn.^,
etc.
fluid are
in the solid,
r^'dJV'Ds',
]
r^'
dN' Ds',
\
J
(363)
where
/',
com
Now,
= const.
/>,
(364)
We may
from
(360).
we
multiply (362) by
for
the whole surface of the solid and for the fluid in contact with
we
y*> SDv
If
(365)
by means of
we may
we add equations (363) multiplied respectively by and take the integrals, we obtain the equation
848
J.
TT'T
(xlhhs
/Svf/stances.
2,rM,<Wm,
/^\(//,r/) SA^'Bs',
(866)
(360).
by means of wliicli we may eliminate the last integral from The condition of equilibrium is thus reduced to the form
///^ 2' ( JTx, S ^,) d.c' dy' dz' +ff/g F' Sz dxf dy' dz + y fv, dN' Ds' ft SN' Us ^f2y {a8x^ /i 6y \ y 6z) Ds ^fpi\.,SN'Bs' /^\ (/',^V) QN' Bs'^^, (867)
//v,
in whicli
and
in
and
if
//j,
//o, etc.
Now
variations,
we
of the solid in the state of reference, yyy'A'x, ^^^A dx' dy' dz'
we have
=fa'
integral in (367)
X^, dx Ds
(868)
with similar expressions for the other parts into which the first may be divided. The condition of equilibrium is
+fff;/
2 {a dx) Bs
0.
+f[ey.tt/y,+pv  ^, {i.iJ\')]6X'Bs'^
It
(369)
throughout
solid
mass
is
not continuous
surfaceintegral in (868),
and
therefore the
surfaceintegral 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
surface.
it
To
is
(370)
Bs'
2 2' {a
X^, dx) f
(37
1)
and
[8^,^trfy,+pv^,{/UJ\')]dX'^0;
and that throughout the internal surfaces of discontinuity
(872)
J.
W. Gihhs
349
(373)
2 2' {a'Xy,,
,+
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 If equilibriitin for a continuous solid under the influence of gravity. we expand the first term, and set the coefficients of 6x^ dy, and 6z
separately equal to zero,
we
dy'
obtain
^I^^
dx'
"^
^"l'
^^' n ^ "^ ~
dz'
'
dY^
dx'
d'^XI
dY^
dy'
(l^\i
dY^
dz'
UjAj'j,
'
'
1^ +
The
first
"dAf
+ ~c' ~
,,
'
''
member
X, Y, Z by the
by
dx' dy'
sum of
the axes
neighlioring elements.
As
it
we have called
is
arbitrarj^,
may
state to
which
x, y, z relate,
^z
i^ince
dsy,
,
^^
dy,
d^,
dy
and
since,
4^ dx
//,
when the
states x,
Z',
and
coincide,
X, Y,
which
Z,
d^,
and
d~
Y^,
represent
difi^er
only by a rotation,
we must have
(375)
X^ =
and
for similar ieasons,
Yy,= The
six quantities
Zy,
Z^
= X,.
(376)
^x,
^^y, ^z,
^y
ovX^
are
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
called the rectangidar
infiiience of
gravity
may
therefore be expressed
by the equations
350
J.
W. Gihhs
dx
dz
,
'
dY^
dZx
where
dl\
dZy
dT,
dZy^
F denotes
Equations (375), (376) are rather to be regarded as expressing necessary relations (when X^^ Z^ are regarded as
bols relate.
. , .
by the
They
will
which
is
not in equilibrium,
which
of
witli
equations (377).
we
cients of
fJir,
we
obtain
{a' {a'
rx,+/i'
J\.,\y' Ty,,)
}
J
(378)
Now
solid,
when
the a\
ft' ,
normal
a'X^,
represents the component
+ ft'X^y'X,,,
^Y
of the force exerted
state
in
(379)
]iarallel to
upon
is
strained
by
the
measured
evident from
the
of which
drawn outward as usual, the same expression taken negatively repreof the force exerted upon the sents the component parallel to surface (per unit of surface measured in the state of reference) by the
Equations (378)
exerted
ujion
force
side
the
and determined by
by
the
J.
Wi Gihbs
351
{a'),
=  {a'),,
=
(/i')
(/),
=
(k%,
we may
also write
etc.,
may
for a surface
Equation (371) expresses the mechanical condition of equilibrium where the solid meets a fluid. It involves the separate
equations
a X,,^
ft'
X +
y'
X=
 ap^^,
}
cx'Y^.^ft' y,.
+ y'Y^,= ftp^,
(381)
the fraction = denoting the ratio of the areas of the same element
JDs
Us
the strained and unstrained states of the solid. These equations evidently express that the force exerted by the
of the surface in
interior of the solid
by the
fluid
surface,
and determined
by the upon the same element of surface. If we wish to replace a and Ds by a\ ft', y\ and the quantities which express the strain of the element, we may make use of the
(but acting in the opposite direction) to the pressure exerted
following considerations.
The product a Ds
is
element
Ds
on the 3 Z plane.
Now
is
indepen
we may suppose
that
it
has any
convenient form.
y'
Let
it
x'
=. const.,
z'
= const.,
const.,
and
let
included by the two others with the surface of the body be denoted
by i, M, and X, or by
and
of
i',
according as
y' Ds'
is
we have
reference
X'
Ds',
and
projections of
plane
Ds upon
M, and
X with
45
Ds
include a solid
figure.
distinguished.
solid figure, the
normal to Ds
falls
normals to X,
III.
M, and
must be outward from the small must fall inward, and vice
May, 1877,
352
versa).
J. 'W.
Gihhs
is
Equillhrium
dz'.
of H'eterhgeneous Substances.
tlie
Noav L'
perpendicular
sides
may
The
projection of
on the YZ
by the coordinates dy
,
dz
dy
,
dz
is
( dy
dz
dz
dy
,
the area of
L\
fdy_ dz __<h_
\ dy' dz'
dy\
if w^e
suppose
moment
and
The
and
same plane
into
will
be obtained by chang(i' ,
ing
y', z'
y'.
a' in
this expression
z', ',
and into
x' , y',
and
three expressions
'2'
may
be substituted for
the three terms
I)s in (3S1).
We
JT',
to denote the
sum of
;',
Y\
Z',
(i. e.,
by changing x
y', z'
into y', z,
and into
z', x',
y',
with similar changes in regard to a', ft', y', and other quantities to denote the sum of the three terms relating to these axes,) and
Y, Z.
This
is
symbols.
With
form
may
be reduced to the
etc.
The formula (372) expresses the additional condition of equilibrium whicli relates to the dissolving of the solid, or its growth without
discontinuity.
If the solid consists entirely of substances
which are
which impede the formation or dissolving of the solid, 6N' may have either positive or negative values, and we must have
fv,
vv,
+V
Vy,
= 2,
{/I
/
,
',
').
(383)
But
if
some
J.
W. Gibbs
353
diY'
is
incapable of positive
and
it
is
iy,tVy,+Py,^:>\{ft^I\').
(384)
reference,
r^,
etc.,
and of the several component substances in the variable state of the solid. We shall obtain, on dividing the equation by Vy
enei'gy, of entropy,
It will
components of the
throughout, or
if
If the
solid is of uniform
composition
we only
If
and the
we may
yu^
composed of
a single substance.
we
use
substance in the
variable state,
reference,)
fluid,
and
F to
we
have
fv,
tl/y,
+J)Vy,=
H^ r',
(3SG)
and
y ~tl/y\J>=:Z l.(J\
(387)
let
To
fix
us apply
it
to the
case of a solid
strain.
If
is
//,
1 1/ \
li
m.
(388)
Now the
a solid meets a fluid require that the traction upon the surface deter
mined by the
face.
This condition
always
satisfied
we
shall
lose
is
nothing in generality,
proposistate
of
reference,
which
which these states are referred being also coincident. normal component of the traction per unit of surface across any surface for which the directioncosines of the normal are , /i, ;/, [compare (379), and for the notation JT^, etc.,
sion, the axes to
We
page
349,]
354
J.
W. Gibhs
/i
Zv
^z),
or,
by
(375), (376),
S=a^X^\f5^Y^J^y^Z^
\2
a f3Xy~\2/3y Yj_
+ 2 y a Z^.
(389)
We
axes.
may
also choose
is
so chosen
is
for the
as
great as for any other surface, and that the direction of the axis of
Y
,,
X)
is
is
as
passing
,1 through the
,
<
axis oi
A.
1^
.>
it
we write
(iS
diS
,
=
CtOt
7
(tfj
^CCJ^
diS
lor
by
treating
and y
as independent variables,
dS
when
and
dS
j
dS
a da
a=l,
is,
p dp \ y dy = 0, ;/ = 0. p = 0,
and
That
^77,
dp
= =
0,
dy
0,
^ 
=
y
0,
when
Hence,
Moreover,
'
nrrl,
A^y
0,
,
P=
and
,
=
0.
0.
Z^ ==
(390)
yr,
dS /^ dp
,,
= + ^dy "K
'
dS
^',
when
a r=
0,
da =:
0,
pdpVydy^(\
and
/:^=1,
i'z
0.
Hence
Therefore,
0.
(391)
when
which are called the principal axes of stress, the rectangular components of the traction across any surface {a,
/i,
y) are
by
(379)
(392)
aXx,
surface,
(1),
PY^,
yZ^.
when the
surface
is
J.
W. Gihhs
355
(2), if
surface
is
perpendicular to the plane containing the two correspondthe traction across any such surface
principal tractions)
all
is
ing axes,
the
equal to
common
(3), if
is
normal and
constant for
It will
surfaces.
in
be observed that
may
be regarded as included
in
the
first,)
but the
always
If,
different.
therefore, a solid
which
is
homogeneous
in nature
and
in state
of
strain is
bounded by
satisfied
may be
by the contact of
will in general
fluids
[see (381),]
which
may
be denoted by
(These pressures
of the solid to dissolve that the potential for the substance of the
solid in the fluids shall
have values
//,', yu/',
fx^" determined
by the
(393)
{'iM)
equations
E
m^
These values,
it
tt/ \p"' v
= fA^"m.
by
(395)
will
nature and state of the solid, and their differences are equal to the
differences of the corresponding pressures divided
the solid.
It
may
temperature
same
solid
write [\,, [f/]j.>, ["]/'? ^"*^ [^'i]/.' for the values which //, would receive on this supposition, we shall have
?;,
v,
and
[4'
f ['/].'
+P'
L"l'
= bu]r'
=n
,
'"
(=^96)
it
[f];,
//!
[n],,
+;V
p' [vl.,
;//
[//
J^ m.
(397)
Now
and entropy
356
J.
W. Gihhs
first
that the
upon the
solid in bringing
stress to the
[]^ evi
dently denotes the work done in displacing a fluid of pressure p surrounding the solid during the operation. Therefore, the first numlier of the equation represents the total work done in bringing
the solid when surrounded by a flxdd of pressure p> from the state of hydrostatic stress p' to the state of stress jt>', p'\ p'". This quantity is
necessarily positive,
p' =i 2^" ^=^p"'
when
If the quantity of
the increase of the potential in the fluid on the side of the solid on
be necessary to
Hence, ///
equilibrium
yWj'"
is
greater than
,and
greater than the value of the potential which would be necessary for
if
That is, (if we 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 Avholly composed of that substance,) the fluids in equilibrium
the solid were subjected to the uniform pressure
all
when
so
that
if
there were present in any one of these fluids any small fragsolid subject to the hydrostatic pressure of
which
is
subject
to
the
distorting
doubtless
facilitate the
commencement
stress
upon its surface, to the same extent, perhaps, body, as if it were itself subject only amorphous an
This
to hydrostatic
it
stress.
may
make
a necessary
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 hydrostatic stress.
But in the case of a crystalline solid, subjected to distorting stresses and in contact with solutions satisfying the conditions deduced above, although crystals of hydrostatic stress would doubtless commence to
J.
W. Gihhs
its
357
t'oini
upon
surface
the
distorting
stresses
and consequent
too
far),
should
be
carried
before
or
on to be formed within the most other bodies, yet within certain limits the relations expressed by equations (39:3)(395) must admit of realization, especially when the solutions are such as can be easily superthey
would
commence
fluid
the
surface
of
saturated.*
It in
may
by equation
(388).
in
To examine
complete generality, we
may
proceed
in the state
of reference
the form of a cube, the edges of which are equal to unity, and
We may
state.
in
of of
in
variable
(This involves
no
loss
generality, since
we may make
we
Let the fluid meet the solid on one or both of the surfaces for which Z' is constant. may suppose these surfaces to remain
We
in
edges in which
axis of JT.
y'
and
remain
]iarallel to
the
It will
fix
the
body
and
do not
It
any way limit its state of strain. follows from the suppositions which we have made that
in
clz
^r= const.
and
==0,
_=
dz
Yy,,
const,
=0,
^ = const. =
dy
(398)
.V
=
f^''
0,
Q,
Zy_,
= 2y~^,.
7
(399)
Hence, by (355),
^ 7 1^7 7 ch...^,.J...+X.4^, +\..d^,
^^^
I
(^^
,
(400)
Again, by (388),
*
The
to the
and
liquid,
was
p.
first
;
See Trans. R. S.
Mufj., S. 4, vol.
57.5
PMl.
xxiv, p. 395.
358
tT.
W. Gibhs
de
(hi
 '/
dt
p dv
dx du
dp
4 in dyi^.
(^01)
Now
made
dz
require that
and
dv
= f,
di/
dii
dz dx r d^, dz dx
,
dz
dx
dy
^1
dx du dz /, d dx dy dz
.,
403)
Combining equations (400), (401), and (403), and ohservino that fy, and //v, are equivalent to f and /;, Ave obtain
;;
dt
V dp
'^
f
Tn
df.i^
,
dy dz\ ^dx
,^
.dx
/^^
dz
dx\ ^dy
all
T.rw ("^'
sides
when
the solid
is
subjected on
to the uniform normal pressure p, the coefficients of the difterentials For the expresin the second member of this equation will vanish.
sion
dy
^,
^ri
dz
by p
it
e., it
be equal to
JTx,
taken negatively.
The
case
is
d^,
and
A\.,
evidently denotes a force tangential to the surface on which it acts. It will also be observed, that if we regard the forces acting upon the
sides of the solid parallelopiped as
pres
sure
^>
by these additional
forces
member
of the equation.
We
We
Vpdp
mass of the
dt
\
m djA^ = 0,
fluid.
(405)
denoting the entropy and volume of the /^F and Wf obtain tion we
By
subtrac
{Vv
V) dt
,
(vf
y)
dp
dx
/
/^
Now
if
dy dz\ jdx
rTr
dz
dx\ dy
UjQt
^
Uj%I
whicli
is
J.
W. Gibhs
359
VvV
(407)
Q
if
where
should
the solid
body
2J<'iss
pressure.
This equation
j
ally be the same as if the solid were subject on all sides to the uniform normal pressure p for the quantities v and ?; (and therefore Q) will in general have different values. But when the pressures on
;
all
sides are
will
dp
cloC
(A/tJ
be the same,
normal and
as constant,
still
equal on
all sides,
j,
Ct'iJ
(XiJ
But
if
we wish
is
to
know how
the temperature
is
sure between the solid and fluid remains constant, but the strain of
the solid
varied in any
t
way
differential coefiicients of
by equation
fit
(406).
These
ftnc
differential
when
the pressures on
y,
all sides
ffni*
when
=
^
j,
are con
ishes only
when the pressures on all sides are normal and equal, vanwhen 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
(f) is
But by equation
and
(92)
/^f =_(^r
terms, and multiplying
feV" ={4^T
preceding
(409)
equation, transposing
by m, we obtain
all
*
etc.,
suflBxed
except such as
may
coefficient.
46
May,
1877.
360
J. TFI
Gihbs
m.i^By
/ dti Y^'^
)
1,
\dni J /
 m /(
dv
p,
\am
Y"^^
I
/ 1,
'p,
m
//f
dp
+ in
v^
dfi.
0.
(410)
we may
and
dv
obtain an equation
we
shall
have the
expressions
w(^ Y^ \dm / p, m
I
/ di]
^ and
m(I 
i,
\am i/t,
)
Y^
p,
m'
The
Avill
We may
fluid
which
2^ oi*
the quantities
constant.
If
'C,
~,
are varied,
the
temperature remaining
we know
sented by
several components
m ^^
m^, m^,
is
etc.,
Now
in
considering variations
will be sufficient if
we make
have
all
but
^
We
may
therefore give to
shall
also constant,
we
dp
TO
M + r, \dm/t,
dm^
p, TO
^1
Xdm^/t,
p,
dm^
+ etc.
containing
dt,
we
obtain
\dph,7n
\dm/t,p.m
+ '" (*i)<,
^^
/du,\^^
,, .
*"=
(lv,
/ ^^
''"
= (^ +
dz
/ ^^
dy dz\ ^dx
'"
<^'
<) "ii^'
.^^
.
+Av,<?^,+
^dx
+ /'^,;^,)"!^,.
,
dx\
.dy
(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
(I'X/ (%Q^>
^)%i
solid)
which
/;,
or of
j,,
v i
with
re
'T.
^Y.
Gihhs
361
may
pend 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 lelation existing between the quantities
which have been represented by
fy,,
Vy<>
^" ^"
'
'''^
'
>
^''
and
z.
When
the solid
is in
))r())lems relating to
the equilibiium of
among
themselves.
sofid is capable,
it is
If in
homogeneous
dz
?
in its
nature and in
of reference,
state of strain,
relation
z'.
we may choose
fy/,
'/.
and the
cc',
between
dx t/ dx
"i dz'
will
be
independent of
But it is not always possible, even in the homogeneous in nature, to bring all the elements simultaneously into the same state of strain. It would not
y\
case of bodies Avhich are
in the case of a
Prince Riipert's
fy*
,
droj). 70
however, we
know
'/v
j,
for
reference,
we may
derive from
For
first
if x',
y\
z'
denote the
state of reference,
in
and
reference,
we
shall
have necessarily
dx
^ = d^'W^
and
if
dx dx"
dx dy"
dy" tc'
+ d^' dx'
,
dx
dz"
'
(412)
y", z")
we
write
its
(,",
divided by
y\
dx"
dz'
z'),
we
shall
have
iM
dx'
dx"^
dy'
R=z
dy^
dx'
(i/
dy'
d2![
dy"
(413)
dz'
dz!^
<M
dx'
dy'
dz'
362
J. Tf^
Gihhs
(414)
Sy, in
If, tlien,
we
liave ascertained
terms
dm'
dz
. . .
of
7/v,,
^,
^,,
and the quantities which express the composithe substitution of the vahies given in (412).
by
.
we
shall
,,
obtam
e^,,
in
terms of
dx
?/v,
dz
.
. .
^,
^,,
^o
dx"
dz"
and the quantities which express the composition of the body. We may apply this to the elements of a body which may be varia
and state of strain in a given 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
ble from point to point in composition
state of reference {x",
y\
s"),
and
if
the
solid of the
same composition,
,
is
known
its
in
terms of
//y,,
dx
y
,
dz
,
.
^,
composition, to
bring
it
y', z')
into a similar
and
similarly situated state of strain with that of the element of the non
dx"
dz"
. .
=^,
as
known
z^\
is,
as
known
^,
,
.
in
terms of x\ y",
p,
^
We
shall then
have
fy"
ii^i
terms of
?/v,
x",y",z"
and and
body
is
known
in
terms of
the density,
of the
if
homogeneous body
solid
of reference
{x', y',
.;'),
this is
sufficient for
nonhomogeneous
An
fy,,
i/y,,
^,
...
^,
involving
that
is
which the same relations may be deduced, may be called a pmdamentcd 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
fv,
'/v5
7^/
'
^t
^^
J.
W. Gihhs
363
^z.
A'x,,
will
relations
dx"
'
'
'
di'
^'
^"
'"
^^^^^
which are
all
may
If we use the symbol ?/>, to denote the value of (as defined on pages 144, 145) for any element of a solid divided by the volume of the element in the state of reference, we shall have
//
^V,=
The equation
(356)
fv,
^7/v,.
(416)
may
6t
Thei'cfore, if
y,
,
;a, St
(417)
we know
,
the value of
in
t,
y,
the body,
. . .
we may
pendent relations
we
shall
have
if\,
by differentiation the values of 7/v J^xt same variables. This will make eleven indebetween the same quantities as before, except that instead of Sy,. Or if we eliminate ify, by means
obtain
of equation (416),
tion of the body.
we
An
value of
i/'v,
y^,
,
,
and the
which express the composition of the body when it is capable of continu.ous variation, is a fundamental equation for the kind of solid to which it relates.
quantities
we
it is
whole mass
(//")
in question,
be uniform throughout the and that the variation of the forcefunction be null or negative for any variation
its
of the
same mass
shall
in
temperature.
We
might have
solid
is
//
for
364
J. TT\
Gibhs
function of the tem]>eratnre and the state of strain, so that for constant temperature
we
"""
the quantities A'x,
,
.
= ^^'(^4)'
by
this
equation.
,
.
This
^z
and
not aifect their values, for this equation holds true of A'x.
as defined
Zy_,
by equation
{'355).
With such
data,
by
transfor
It is
would be that
//y,
e^,,
Such a method
The method
more
distinctly
the role 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
dynamical problems
note on page 145.)
in
method can be more naturally extended to which the temperature is constant. (See
We have
Hence,
it
must be
possi
by
six functions of
dx
;,
^,
dz
quantities
For these
we may choose
by the
have
we denote
these quanti
by A, B,
C, a,
b, c,
we
shall
Thomson and
i,
705.
With regard
"
compare
also
Thomson's
Memoir
On
p.
ligiit
J'ransactions of the
Cambridge
J. TF. (jrlhbs
365
<)
^'''^
is
,
^,/dxdx\
^=^W^'>
The determination
C, a,
b, c,
^=^\d^'dx'}
thus
7i,
A,
A,
i>,
C, a,
b, c.
can
and
t/y,,
or of
i/\,
and
t,
is
capadis
any given strain of an element there are three lines in the element which are at right angles to one another both in its inistrained and in its strained
state.
is
isotropic,
//y,
tion
must with
i/\,.
or
with
determine
tlie
value of
To demonstrate
,...,, we may
any
line of
is
proceed as
<t',
fol
The
ratio of elongation r of
which
/i',
y' are
evidently given
by
/dx
dx
dx
A2
(dz
dz
^,
dz
A2
Now
is
always possible to give such directions to the two systems of rectangular axes JT', Y\ Z', and X, Y, Z, that
is
that
dx
(421)
We may
allel
is
at
to this line in
any other, and make the axes of .Tand A"' parthe strained and unstrained states respectively.
.366
J.
/Substances.
Moreover,
if
we
f/fr^)
(:?(r)
,
,
write A^r
da
d{r^\
for
rv',
the
/J',
difFerential
coefii
cients obtained
y'
as
itidependent
variables,
when
and
'
<?^v'
+
1,
/J'
r7/f f
;/'
dy' =z
;/'
0,
' z=
/i'
0,
;=
0.
That
IS,
A.y^O,
'
and
/i'
AJ
0,
== 0,
when
Hence,
1,
y'
=
0.
0.
dx
^,=
dx
0,
^.
(423)
is
perall
such lines
X' is perpendicular to JY" in the strained state. we may choose one for whicli the value of r is at
any
other,
Of
least as
gi'eat as for
this line in
Then
,,
= 0.
(424)
and
it
may
easily
just been
employed that
1=
will therefore
0.
,42.)
Y\
and Z'
the unstrained
body
be parallel to
JT, Y,
and
Z
dz
in the strained
body, and
dx
dx'
'
dy
dy'
'
dz'
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 r^ is reduced by
These
lines
viz..
J.
W. Gibbs
367
ceed to find the relations between the ratios of elongation for these dz dx rj lines (the Jor^?tc^/:>/ axes of strain) and the quantities y^, ,
.
strain
we have
when
a' da'
0,
mined from
(420) as before.
1 c?(r2)
Therefore,
1
'ft'
a'
1i^
_ ~
d{r^)
"dj^
_ ~
l_
d{r^)
'
(426)
y' dy'
From
(420)
we obtain
directly
da
dft'
(427)
2
dy'
necessary relation
From
a' 2
the
ft'2
two
_^ y'2
last
i^
we obtain
^
^d{r^)
dft'
^^
'
'
^ dy'
r'
(428)
or, if
we
from (420),
If
we
368
J.
W. Gibbs
write
We may
Then
0.
(431)
(432)
Also
F
(
(dx dx
\dxi)
j
/dx
dx\)
S
\dy'J
2
\dx' dy'j
/dx
/dx
dx dx
/dx
dx\\_
<^y
(^'^
2'^
y
,
/cfe
\2
6fe
c?c
dx dz dz^\
~^W/
\dy')
~dx'dy'd^'dy'~dx'dy'd^dy']
t?.K f?a;
]
z=i2'2
dx c
YY^^y \^
^') dx'
(dy y/dx
This
may
also
be written
dx
dx
dy'
(434)
F=i
^'
dx'
dy
dx'
dy
dy'
it
will
symbol
^
3
+3
X, y, z, into y,
symbol
2
33
;
in the
x, z, x, y; x, z, y; y, x, z; and z, y, x; and the same sense except that the last three terms are to
be taken negatively
to
x', y,' z'
also to use
z'
and
2' in a similar sense with respect 33 as equivalent to x', y', z', except that
they are not to be affected by the sign of summation. understanding we may write
With
this
G= 33
:^'
/dx dx\
\dl' d^'J
/dx dx
/dx dx \
\d^' dz')
\dy' dy'j
(435)
* The values of
and
deduced
at length,
may be
Introductory
usual theorems relating to the multiplication of determinants. See Salmon's Lessona to the Modern Higher Algebra^ 2d Ed., Lesson III; or Baltzer's Theorie und
der Determi'aanten^
5,
Anwendung
J.
W. Gihhs
369
In expanding
the product of the three sums, we may cancel on account of the sign ^' the terms which do not contain all the three
33 expressions dx, dy, and dz.
^
^
(
^
3+3
dx dy dz
/dx dy dz
(dx dy dz
870
J.
W. Gibhs
singlevalued function of
E^ E, and H.
The determination of
is
therefore reduced to
the determination of this function, or (as appears from similar considerations) the determination of
It
//\
,
as a function of
t,
E^ E, and H.
appears from equations (489) that represents the sum of the squares of the ratios of elongation for the principal axes of strain,
that ^represents the
for the three surfaces determined
sum of the squares of the ratios of enlargement by these axes, and that G repreAgain, equaeqiiation
ratios of
;
shows that
E represents
(434)
X', 1", and Z'; shows that J^ represents the sum of the squares of the
Y\
Y'Z\ Z'X'
and equation
shows that
coordinate axes
is
arbitrary,
it
sum
of the squares of
which
Hence,
one another,
is
of
the
lines
or surfaces.
^^and ^F
are the
mean squares
possible directions in
There
is
is
in
terms of ^,
^,
l)ut
there
is
also a
E^ F^ H.
it
If the sys
X\ Y\
will
always be
convenient to suppose, the determinant TI will always have a positive value for
possible to give to
shall
which a l>ody can be capable. But it x\ y\ z' that have a negative value. For example, we may make
any
strain of
a*,
is
X
This
will give
=
1,
x',
= y\
y r= y\
=
z

s'.
(440)
I[t=
while
a.',
X :=
will give
=z
z'
(441
11=
1.
\.
Now
although
such a change in the position of the jjarticles of a body as is represented by (440) cannot take place wliil(> the body remains solid, yet
J.
W. Gihhs
371
a method
of representing
may be
considered incomplete,
We may
the state
avoid
all
sent a strain.
(a?',
Let us
call
by (440) and (441). such confusion by using E, 1\ and II to repreconsider an element of the body strained which in
a cube with
c^a?',
X\ Y\
which
y\ Z\ and
z') is
its
the edges
y\ or
dz'
Whatever
2)
may
(,t, ?/,
which
dy\
and
~,
^
it
to the
shall
in whicli the
1",
edges
ffe',
dy'
may be done
parallelopiped
and therefore without changing the sign of H. Now tw^o cases are possible the positive end of the edge ffe' may be turned toward the positive or toward the negative direction of the axis of Z. In the
;
first
case,
is
evidently positive;
in
The
we
y, z) to the
y\
z')
its
volume the
value zero.
If
we now
and denote by
C/j,
U2',
U^
for example,
and unstrained element respectively, it is evident that the sign of r., depends upon tlie direction in U^^ which Ave regard as
corresponding to a given direction in JJ^.
positive or negative value of
If
we choose
all
to associate
be positive, the
will determine
axes
t^j,
?7j',
U^,
Or,
f/3
is
or
is
tem
coincide.
we
two systems
will deter
of axes, so that they shall be capable of superposition, correspondinodirections coinciding, the positive or negative value of
we may
write
372
tT.
Wi Gibhs
= H=
J.
W.
Gibbs
373
values to
//v/,
etc.,
denote by r^ the
stresses vanish at
when the stresses in the solid vanish. If we common value of rj, r2, r^ which will make the
by equation
(444) to be expressed in
of
rpy,
and
''i^o,
it is
^2^0.
That
is,
''a'^o.
(446)
given by equation (444) are of the same order of magnitude as the cubes of the above diiferences.
dlj:y,
The
dipy,
dr^
will
'
dr^
dr^
differences.
_ dipy, dr^
dr.
^
dipy.dr^
dr..
dipy,
dr..
dr^
<dx
dr^ji
jIx
<^^r>
d^.
Ax
ci^n
^'
ax
dx
dx
dx
tion (444),
whether we regard the true value of ipy, or the value given by equaand since the error in (444) does Jiot affect the values of
dr.
AJjvU
dr^
J.tJC'
dr..
~.\A/iMj
dx'
dx'
dx'
which we may regard as determined by equations (431), (432), (434), (437) and (438), the errors in the values of A'x, derived from (444) will be of the same order of magnitude as the squares of the differences in (446). The same will be true with respect to A\,, X^,, Yy^,
,
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 If we denote by isotropic solids. and the elasticity of volume
determined under the condition of constant temperature and for states of vanishing stress), we shall liave as
rigidity'^ (both
and the
definitions
^'^~''\)t'
* See
^^^"^
= r,^v',
i,
(448)
Thomson and
p. 711.
3*74
J.
W. Gibhs
where
V
its
j^
subjected,
volume, and
volume
in
and
dx
f&y
(449)
\
when
^_^_^_,.
dx ^^dx
dy'
dz'
is
dy
dz'
di/
dz
dx'
dz
j
dx'
dy'
'
Now
we
when
the solid
all
sides, if
consider so
much
of
as has the
volume unity
1
in the state of
reference,
we
shall
have
r,
=r
i
=:
rg
=: y^,
(450)
(430),
if\;
= +3
e /'^
+ 3/ 0^ + h V.
//,
(451)
Hence, by equation
~^'
= (M)t == 2
e ^'^
+ ifvi + ^
i/.i;
(452)
^,(^)^=t6^)* +
and by (448);
(453)
Frrt^ +
'
1/V,,
(454)
(449),
(432),
To obtain the value of Ji in accordance with the definition given by equations we may suppose the values of E, F^ and
(434),
in equation (444),
R
i^zz:
2e
4/r^,2.
Moreover, since
^ must
vanish in (452)
when
= r^^, we have
(45G)
e, /',
2e
+ 4/r2+A,.^:^0.
may
be obtained the values of
From
A, in
R\
viz.,
The quantity
r^, like
and V,
is
differential coefficient
^'*
when without
J. TF.
Gihhs
3V5
It will
case
is
not be necessary to discuss equation (443) at length, as the which has just been treated. [It
bi
the elasticity of volume and the rigidity, both determined under the condition of constant entropy, (i. e., of no
stiess, Ave
shall
F'=~;t7^'
+ I/'^o,
0.
(458)
e'
(459) (460)
Whence
P^'^r,V'
In these equations
r,,,
^,_R'+^r,V'
f'=~~Vl^'^
^ _ I^ ^^'=^j^,
(461)
R', and
the quantity
If
i/y,.
we wish
made.
isotropic), the
changes required
If
in
the fundamental
of
its
equation
are
easily
any
length in the
we change from
,
first
,
y,, ?/v,
are divided
by
a^,
E by
a"^
and that of
E by
a*.
In
of the
state of reference,
we must
r<3//v,, ci^E, a^F, a^H for //,,, E, F, and H, respectively. In the fundamental equation of the form (443), we must make the analogous substitutions, and also substitute a^7]x,
for
7/v,.
[It will
i]y,,
be remembered that
it is
i',
e',f',
and
Jt
represent funcijy,
tions of
and that
are
sul)stitiited,
There are certain bodies which are solid with respect to some of have other components which are fluid.
we
shall suppose
which can
i.
e.,
we
shall sup
48
June, 1877.
376
J.W.
Gibhs
components except such as vanisli 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
such a body,
in a
when the
Let 7',,', 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
other words, let these symbols denote the which the several fluid components would have, if the body should be brought to the state of reference while the matter contained in each element remained unchanged. We may then say that
densities
state of reference, or, in
when
/"',
/"/, etc.,
are constant.
The
fyi
will therefoie
be given by an
t di],.,
\:2 2'
Ix^.
is
etc.
(462)
Now when
this
the
body
equation
(^Y
its
reduce to
joc^Uvi
elsewhere,
divided by
volume
in the state
:2:e
dx
dx'
dy'
dz'
j> d
dy
dx
dz
dx'
dy
dy'
dy
dz'
dz
dy'
dz
dz'
=
We have, therefore,
dsy,
2^ dvy,.
(464)
d)]y,
2^ <Jvy,
L,,
drj
Z^ dl]! f
in
etc.,
(465)
ence,
and multiplying by the volume of the element which we may regard as constant,
de
di]
J) dv
\
L dm^,
(466)
J. TF.
Gibbs
377
where
f,
//,
It is
The
body
to
which
tlie
symbols relate
state
shall
matter.
otherwise.
The varied
may be
is
and the
solid
considered invariable,
we have by equation
yi/
(12)
de =^
It
ih]
jo dv
\
dm,,
//,,
dmi,
f
etc.
(467)
which relates only to bodies of hydrostatic stress, so that the 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 i, X^, etc., when determined for a state of hydrosion
//,
//,,,
etc.
Since
we have
we may apply
fliiid
is
this
term as we
in the
body
one of hydrostatic
former definition.
then be written
It will also
symbol
Equation (462)
may
f?fv
dih,
pi
drj +
/x,,
dl\'
etc.
(468)
any limitation with respect to the initial state or to the vaiiations, except that the solid matter to which the symbols relate shall remain
the same.
evident in the
first
place that
if
etc.,
constant,
we
shall obtain
ditions
expressed by the formulae (364), (374), (380), (382)(384). The quantities /',', F^, ^tc, in the last two formulae include of course
378
J.
TK Gibbs
by /"', jTj', etc., and which components of the body, as well as the correspondits
Again,
if
we
sup
will easily
substances which form the fluid components of the solid body must
satisfy the
same conditions
in the solid
body and
in
tact with
it,
The above conditions must however be to make them sufticient for equilibrium.
solid is dissolved at its surface, the fluid
free
may
in like
manner
and com
may
body
body or
not,)
an
equation of the form (383) must be satisfied, in which the potentials /7, /^; etc., contained implicitly in the second member of the equation are determined from the solid l)ody.
Also
if
body
components
the
as in
must be
satisfied,
The
quantities
t,
X^,,
Z^,,
^y.
/<,
/<,
etc.,
(409)
^^'
"!" ^
^^^''
^'''
('^'^
= ^
dx'
etc.
(471)
This
iesult
may
be generalized as follows.
Not
only
its
is
the second
member
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 symbol '2 '2' is here supposed to be expanded into nine terms), and For to to at the same time change the sign of the term from
J.
W. Gibbs
379
substitute
^]^i,(Jt
example,
>/y,).
is
equiA'alent to subtractif
iug
tlie
Therefore,
we
consider the
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
<puintities in (409)
the remaining quantity of the second pair with respect to the inde
first,
taken positively,
if
the independent
by the
sign
in
equation
Thus
dx'
^\lx'
WJx  [dxj,,:
where
in
\di
;;rx,
~
\dx;Jr.:
'
^^'^'
or
//y,
either
Ay, or 
It will
\
(^*'
either
ry
dz
Zj,,
or y;, eitiier
//^
or /
^,,
,/,
etc.
is
ditions
//.,
= const.,
Ff,',
//,,
= const,
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
in
when FJ,
etc.,
any
infinitesimal
are constant, the heat absorbed by the body change of condition per unit of volume measured
is
represented by
tdi]^,,.
If
we denote
this
no
/^og_A
\
_((IX^\
d^ )q~ UQv.)':^.'
/^oi_\ \ dX^, }q
_ 
('1^\
\dQjxJ
\d\o^t)%,^
^^^^^
\dxJtvi\ogt)x.:
where ZV, F/,
etc.,
\/lt^'dx'
^^^'')
must be regarded
. . .
either Z^, or

,
in
each equation.
380
J.
W. Gihhs
Influence of sukfaces of discontinuity upon the equilibrium OF heterogeneous masses. Theory of capillauity.
We
in treatiiig
of lieterogeneous masses in
might be considered as separated by mathematical surfaces, each mass being uuaifected by the vicinity of the others, so that it might be homogeneous quite up to tlie separating surfaces
contact, that tliey
its
various components
and
such
if it
That
could
is
any mass
sensibly affected
by
its
natural
and
possible a simple
We may
term
may be
which
crise
in a fluid mass and uninfluenced by gravity. For the premeasurement of the quantities with which we have to do, it will
is
in equilibrium
For
and
all
and imagine a geometrical surface to pass through this point other points which are similarly situated with respect to the
of the adjacent matter.
condition
all
We will
J.
W. Gihbs
tliis
381
form of
as there
any want of perfect homogeneity in the fluid masses, the closed surface is such as may be generated by a moving normal to S.
is
by s. Moreover, let the s, 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,
this portion
denoted by
is
lie
entirely
beyond the
infliience
of
Let us
which contains
the surface s (with the physical surface of discontinuity) M, and the homogeneous parts M' and M", and distinguish by f, i', t\ if, //', 7/', m,, m^\ *'*/, *'*2? ^25 ^"2'? ^^c, the energies and entropies of these masses, and the quantities which they contain of their various components.
It
is
more
precisely
what
is
to be
understood in cases like the present by the energy of masses which are only se])arated from other masses by imaginary surfaces. A part
of the total energy which belongs to the matter in the vicinity of the
referable to either
and such energy is not in the nature of things mass by itself. Yet, to avoid the necessity of
it
will often
be convenient to
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 imiform 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
in the energies
that
of
the surface which cuts at right angles the nonhomogeneous film (apart from the consideration that without any important loss of
generality
we may regard
no change
But
in the variations to
the masses
do not create any discontinuity at the surfaces bounding 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
382
(T.
Wl Gibhs
the total
(juantity,
amount of energy.
To show
is
that
it
we have
if
an infinitesimal discontinuity of
is greater as determined by this rule tlian if determined by any other (suitable) rule, the energy of the mass on the other side must be less by the same amount when determiued 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
first.
considered
we may suppose
a similar
method to
With
M, M', and
JNI".
We
shall
suppose
due to any want of perfect mobility of the components by means of which we express the composition of the masses, and that these components are independent, i. e., that no one of them can be formed out
of the others.
With regard
tinuity,
it
to the
sui"fixce
of discon
is
variations
(i.
e.,
various components.
mass will not affect the energy or the entropy of the surrounding masses (when these quantities are estimated on the princi]>le which we have adopted), and it may therefore be treated as an isolated system. For fixed boundaries of the mass ]\r,
this
and
(470)
where
^If,,
A^, A2,
by the
initial
is
evident that
A^
the
IJy com])arison
yl
,,
will
homo
J.
W. Gibhs
383
By
a natural ex
we may
fact,
call
This designation
will
which
will
is
ielate.
we may
f ;/.
write
de =zt6f^\If
jii^
dm
(Jw,
+
;*
etc.
(477)
we
substitue
for
in this equation,
true of
all
member
in
of
which
its
entropy or of the
quantities of
It is
rf//,
various components.
important, however, to observe that for any given values of 6m ^, 6m2, etc., while there )naij be possible variations of the
for
is
member
* To illustrate the difference between variations which are reversible, and those
which are
rium
at a
not,
we may
mixed.
We may also
conceive of
them
as
mixed
is
of mixture
where they meet, and then the amount capable of variation both by increase and by diminution. But when they
amount
diminution, and
it is
to mix) should
be greater than
the second
member
of (477).
;
but
it
may be
is
here used
is
en
tirely
different
from that
in
which
it
is
to a state
state
may
from the
B is B to
the state
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
that
is
bears to B.
49
June, 1877.
384
It will
J.
TT'T
Gihhs
EqxdUhrlum
of Heterogeneous
ISuhstances.
press this
by an
equation.
e.,
the
value nearest to
oo)
of de consistent with
Sj]
\ lA^
diti^ \
/.(^
Sm.^
+ etc.
(478)
consists of
For the internal equilibrium of the whole mass which the parts M, M', M", it is necessary that
6e\ St'
for all variations
+ Se"^0
(479)
which do not
we also regard the surfaces separating M, M', and M" as invariable, we may derive from this condition, by equations (478) and (12),
If
+ ^tc. + 61/ //j' Sin^' + /'o' + etc. dill/' /i/ ^"i/ + etc.^0, + (h/" + /</' +
6?/
\ /fj
\
d7)i^ \
J.I2
Sni^
t'
<Si>i2'
t"
(480)
dm^
61^2
etc.
f
\
dm/ + dm/ =
6111/
J
0,
6)112" ^^ ^5
I
It
may
these quantities relate are not actual or possible components of M' (Seepage 117.) To satisfy the above condition it is necesor M".
= t'
t",
(482)
jji/'
6m/^).i^6m/,
that,
if
1.1/'
67n
/'^
f.12
^^^2%
^tc.
/(,, for
(484)
instance,
It will
be observed
is
an actual component of each of the homogeneous masses, relates If it is an actual component of the yu/ ///'. we shall have //,
first
possible
If it is also a //,'. we shall have yu, component of the second homogeneous mass, we shall also If this substance occurs only at the surface of dis
have
/A^=}.i/'.
J.
W. Gihhs
385
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
relatiiig
to
tem2)erature
and
the potentials
which we have
befoie
by
bounded
limits of
like
homogeneity,
condition which
may be
It
fulfilled
by
sur
films,
which separate such homogeneous masses. The properties of such which are of course different from those of homogeneous
into
The volume occu)ied by the mass M is divided by the surface two parts, which we will call '" 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 com
respectively.
We
shall
then have,
by equation
(12), if
t'
we regard
= de"" =
Se'"
Si:"'
ch/"
+
+
//,'
(hn^'"
j.i^
dm^"'
etc.,
(485)
;
t"
6i/"'
///' (h,i^""
+
iA
f.1^"
Srn.J'"
+ etc.
(48G)
whence, by (482)(484),
t
we have
//,
(U""
Sm.J"
etc.,
(48V) (488)
\ /.i^
6m2'"'
+ etc.
From
we have
S{e
t'"
t rf(//
//'"
//'")
//,
rf(w,
m,'"
m,"")
f /t2
+ etc, (489)
(490)
etc.,
Or,
if
we
set*
f "",
if
= 7/
//'"
;/"",
m\=zm^ rn^" ^
m^"",
(491)
is
here used
is
The Roman
386
J.
W. Gibhs
write
St^
JEquilihrimn
t
of Heterof/eneoiis Substances.
we may
(h/^
//
ih/f^
//2 c^?"
etc.
(492)
This
is
be observed that
a^
denotes the
excess of the energy of the actual mass which occupies the total
it
would
same uniform value quite up to that surface which it has at a sensiand that tf, m^, m, etc., have analogous significations. It will be convenient, and need not be a source of any misconception, to call 6* and ?f the energy and entropy of the surface
(or the siijierficial energy
and entropy),
in
and
sities
,
171^
~, etc.,
Now
these quantities
[e^,
if,
m\,
etc.) are
determined partly by
we
surfaces
by means
The
will be
remembered, 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
To
we have
all
Let us
its
fii'st
suppose
position in space to
will
necessary to
by translation or rotation. No change in (492) make it valid in this case. For the equation is
is
be
if
valid
varied in position
also, if
the material system and s are both varied in position, while their
relative position
remains unchanged.
its position.
Therefore,
it
will be valid if
But
if
we must add
to the second
member
dtp" ~~ jA
Srn^^
~
s.
f^
Sm% ~
If
^^^c.
in
the form of
we
su]pose s to be
suffi
J.
W. Gibbs
887
and
above expression will be determined hy the variation of its area 6s and the variations of its principal curvatures (Jc^ and (Jcg, and we
may
write
St^ =.
t
Sif f
/<, 8tiii\
\
//g
dm\
^
+
or
8t^
a 8s
6\ 8c
+ etc. + C'g
(Jc2,
(493)
= +
6ff
yUi Stn^^
4/^2 ^^"%
^^^
ff
+ i{C\
 C,)8{c,c,),{494)
s.
<j,
C,, and
initial state
above
is
But
it
is
surface s that 6\
C.^ shall
To show
de
8?/
t
8e"'
81/"
t
_ Se"" +
=
i.
etc. //g 8711 ^"' ^" + etc. /z, 8711 8m + + //, ^"" 8?/"" + //, 8m + /1 2 8m.^ "" + etc.
/J
^
8m^
o8s^i
{C\
+
8m
C,) 8{c,
(12),
c,)
i{C\ 
(J,)
8{c^~c,), (495)
e.,
by (482)(484) and
8e
87}
^x^
<2
^^2
r^)
^^c.
+H
 O2)
^(c,
c,).
(496)
appears
the same in the two homogeneous masses separated by a plane surFor let us imagine the material system to face of discontinuity.
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
//j
//g
etc.
0.
Also
8s
0,
0,
0,
8v"".
Hence j)'
in the
is
Let us now examine the effect of different positions of the surface !^ same material system upon the value of 6',  (', supposing at first that in the initial state of the system the surface of discontinuity
is
plane.
Tn the
388
J.
W. Gibhs
Equilibrium
tliis
of Heterogeneous
Siihstances.
initial state of
the system
is
parallel.
In the
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
varied state of the system, let
it
;
(Such a variation
the system
as
may
tively,
the
surface
may
side.
But
whether such
librium
is
a variation is consistent
Let the
by the symbol
s'.
Without
initial
us
make another
face s.
tion
be parallel to
its
former posilie
the
same distance
It will
of course
lie
unvaried system.
s,
perimeters of
'
by a common normal.
Now
the vahie of
in
equation (496)
is
s,
being deter
the same
is
member
Moreover, ^(Cj
Cg) =
both for
s'
s'
and
s".
If
we
and
for s"
by
the
marks
and
",
we may
therefore write
Now
we
if
we make
Ss"
z=z 0,
shall
J.
W. Gihbs
389
Hence
But
Therefore,
tf(e,'+c'./)r=dXc/+C2").
6*/ +
^'3
'
+2
tf'.s
= 6\
"
C\ ".
tliat
we may give
is
G ^" +
it
sufficient
other side of
plane,
Since this
true
when
is
must
also
nearly plane.
And
when
for
may be regarded
This
is
as nearly plane,
the
nonhomogeneous
have any sensible
discontinuity
so that Cj
is
film.
size.
the case
when the
radii of curvature
plane or curved
is
Now we may
is
by equation
1,
(498) that
if
the quantity
is
same order of magnitude as the values of 6^, 7f, ni\, //<, etc., while the values of C, and G2 ai"e of the same order of magnitude
the values of the former quantities caused
as the changes in
by
by
unity.
can be very
little
in s, the values of
o'.
C, and G^
if s'
must
in general
And
hence,
be
Avill
make Cj"
f C\" vanish must be very small (of the same order of magnitude as the thickness of the nonhomogeneous film). The position of s, therefore, which will make G 4 G2 in (494) vanish, will
^
in
general
be
sensibly
coincident
with the
physical
surface
of
discontiniiity.
We
is
not distinctly
indicated that the surface s, in the unvaried state of the system, has
It will
be remembered that
we have
called the
cUvidmg
surface
is
surface,
and which
is
of discontinuity.
is
We may
everywhere determined by similar considerations. This evidently consistent with the suppositions made on page 380 with
390
J.
TK Gibbs
We
may
in (494).
it
will
be observed that
is
Cj
= Cg, which
Now
the case
when
is
plane.
on account of the
it
as
composed of parts which are a})proximately plane. Therefore, without danger of sensible error, we may also cancel the term
Equation (494)
6t^
is
t
S)f
+ o 6s+ //
dm^^
(497)
We may
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
dis
homogeneous masses. From the two equations may be directly deduced the conditions of equilibrium of heterogeneous masses in conwithout disregard of the
in
we
shall take
at present
we
we take account
We sup})Ose as before that the mass especially considered is bounded by a surface of which all that lies in the region of nonhomogeneity is such as may be traced by a moving normal to the But instead of dividing the mass as before into dividing surface. four parts, it will be suflicient to regard it as divided into two parts by the dividing suiface. The energy, entropy, etc., of these parts,
estimated on the supposition that
energy,
etc.)
is
its
denoted by e\
^
+ 'f f",
Then the total energy rf, etc., ", ?/', etc. and the general condition of internal equilibrium
d^iH(^i'+(5f"^0,
be
will
be
that
(498)
J.
W. Gibhs
391
when
V^
is fixed, and the total entropy and total components are constant. We may sup]ose
'*^^2'i
'^^''2
1
'"n
"*]'? '"i">
"4'
6s
^t'C,
to be all constant,
Tlien
by (497) and
p
Sv'
 p"
dv"
0.
(499)
(We may
set =: for
^,
two opposite
if
directions.)
membrane without
and having a tension ff, uniform in all directions, existed Hence, the ])articular position which we
for this surface
have chosen
ff
may
move
SN, we
6v'
\
shall
s
have
Sv"
Ss z=
(c
+ C2
s dJV,
= SK
^p' Jo",
=
.s
6JV;
(500)
whence
which
This
a
relates.
{c^
c^)
when
the side to
is
of equality of pressure
119,
flixid
masses
in contact, vvlien
faces of discontimiity.
We
by these
Fundamental
one of equilibrium.
state
is
of Discontinuity.
is
sup[)osed to be
The only
e.,
that an o])po8ite
To
distin
we may
dif' f
f
/^
d7n\
Mz ^''4
^'t<^'
(501)
Both the
may
be neglected,
we
from
any finite value s, while the material system to a part equation relates remains without change, we obtain the which of
zei'o to
f^
f if^
\ (7 s
+ n
m^,
J
//g
n%\ f etc.,
(502)
July, 1877.
50
:592
J.
W.
(irU>hs
Eiuillhrhim
is
^,
of Heterogeneous
ISiihstanees.
whicli
(in
may be
equilibrium) which
//,, f^^i
we
variable,
sdG
\
m\
f?//j
+ m\
diA^
etc.
0.
(503)
If
we denote we have
by
fg? Vs?
l\i
^2>
f^
jf
s
s
,s
r,
==
1,
i ,
= ^,
etc.,
(505)
^^tc,
(506)
"
8^
t^tc,
(507)
7/s
f?yu,
7^2
^tc.
(508)
Now
any
restriction
the temperatx;re and the potentials for actual components shall have
For however
may vary
(on
account of arbitrary variations of the temperature and potentials), and however the superficial tension may vary, equation (500) may
always be
Moreover,
satisfied
to the surface of
is
not great.
any of the potentials /.i^, /.i.^, 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 substances.
The values of
and
it
t,
f.i\>
/*3'
^^^ ^^'^
therefore independently
is
variable,
it
a function of
these quantities.
form of
this function
is
known, we may
/'j,
derive from
by
number
I\,
This will give us, etc. in terms of the variables just mentioned. 2n \ A quantities the between ecpxations independent (507),n3 with
which occur
in
that ecpiation.
These
.are
all
';/f 1
./
W.
<rlJ>hs
393
we may
2^/,
consider
that
tities
we have
y/
+3
+5
quan
occurring in equation
independently
variable.
An
yUj,
//g,
etc.,
(509)
may be
An
equation between
f^
//,
ft',
)ii\
))i\^
etc.,
^^.c,
(510)
('51 1)
or
between
also be called a
fs,
'h>
^H
^s?
may
it is
fundamental e([uation
if this
in
For
may
be regarded as subsist
{
2 of
n.
may
be regarded as independent

for the
and one
we may
obtain
by
differentiation
}
2 additional
equations
between the 2;^ } 5 quantities occurring in (502). Equation (50(3) 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,
\

quantities
may
If
be obtained.
we
set
ij)^
^,
t rf,
d)n\
(512)
we
=.
to
if'
dt
ds\
jx^
\
pi^ dni,2
+ etc.
(513)
An
equation, and
The reader
mental equations, which relate to surfaces of discontinuity, and those relating to homogeneous masses, which have been described on pages
140144.
3 94
J. TF.
Gibbs
On
the
When
all
tinuity are
the substances which are found at a surface of disconcomponents of one or the other of the homogeneous
//g,
may
be determined by means of the relation (500). ments are practically confined to cases in which the difference of the
pressures in the
homogeneous masses
is
small
for
measurement.
since
and
p>"
may
we can make,
that
we must regard
o"
for values of
/.i^, /.(2,
etc.,
which
satisfy
change
in the value of
for variations of
/>'
t^
which are
=:^>".
t,
To show
this
more
distinctly, let
//g,
m^,
etc.
remain constant,
da
d/^i^,
denotmg the
f?y
^ and
Wi,"
__
.
Hence,
dp"
(;/,' y^")dp^,
and But by
(50()
r,
r?(;y
~ p") =
d{c^
(;//'_;/,') da.
(c, f ('2)
da + a
+ C2) +
= (Hp'
j>").
Therefore,
l\
or
{c,
C2) dff
+
^1
r, a d{c,
(i
C2)
= ir,"
;/,') dff,
Ir/'
r/
^2)1
^^=
^\ ^4^1
Cg).
* It is here supposed that the thermodynamic properties of the liomogcneous masses liave already been investigated, and that the fundamental equations of these
J.
W. Gihbs
(Cj
395
Now
Y
i"
[\
c^)
generally be
very small
compared with
y i'.
we have
To
;/,',
^"
as constant.
a'
is
plane.
From
this
it
appears that when the radii of curvature have any sensible magnitude, the value of
o'
same
as
when
the surface
is
the same values, unless the component for which the potential has
densitj'^ in
the
two
homogeneous masses,
variations take place
in
is
Accordingly,
cial density
ficial
we cannot
its
in
l\ from
value
(^
by measurements of superI\,,
\dj.ii/t,fi
tensions.
//s,
The
fg,
same with
F^,
etc.,
and also
with
The
quantities
to admit of direct
%, T\, /'a, etc. are evidently too small in general measurement. When one of the components,
suiface
however,
is
of discontinuity,
it
may
be
more easy to measure its superticial density than its potential. But except in this case, which is of secondary interest, it will generally
be easy to determine
ff
in
terms of
t,
//j,
/.i,
etc.,
with considerable
impossible to
difficult or
An
equation giving a
in
terms of
<,
/<i, yWgi
plane,
may be
ia
all
39(3
J.
W. Gibhs
JEqidllbrititn
of TIeterogentous Substances.
and
tlie
siu'face of discontinuity.
These
results can
be exliibited
The
particular
position
ado])ted
for
the
dividing surface
(which
the
make
term i
C'jj
Cg)
is
(^
(c^
of the surface
ing surface
is
is
evident that equation (501) will hold true for plane surfaces (sup
posed to remain such) without reference to the position of the dividing surfaces, except that
tinuity.
it
shall
We
may
for
None
new symbols,
fg, ?/s,
be affected by such a
m\, m\,
etc.,
as also
F^, F^,
etc.
have
different values
o",
when
choose,
changed.
The quantity
however, which we
may
we
by
For if the dividing surface be moved a distance A measured normally and toward the side to which v" relates,
value by such a change.
the quantities
^s?
Vsj
^15
^25
etc.,
increments
A(fv"fv'),
fv', fv", 'A'',
i]\"
(//v"
//v'),
A(ri"ri'),
^{y/y2),
o"
etc.,
in the
will receive
p"
p'
6v"
jt>'
ey
t //v'
/'i
ri'
Therefore, since
the value of
o'
is
zero.
The value
of
o'
is
ing surface,
when
But when we call this quanwe must remember that it will not have
J.
W. Gibhs
Equilihrmrn of Hetefogeneous
its
S?d>sfa>ices.
397
its
chai'acteristic
trary surface.
C/Onsidered as a tension,
in the surface
strictly speaking,
nowhere
else.
The
however, wliich
sufficiently
we
to
make
It is
this distinction 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 xip to the dividing surface. In other
total quantity of
make any one of 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 dividingwords, Ave
place the dividing surface so as to
5
may
etc.,
vanish.
surface
fail
to
Let us
so placed as to
make F^
0.
Then equation
//s( I) (?
Tsd) f^/<3
etc.,
(514)
by
a dividing surall
1\
0.
Now we may
consider
the differen
second
member
e.,
that
given by equation
/)'
known
yUj
for plane
surfaces in terms of
//j,
/.I2,
etc.,
we can
eliminate
pression
sures,
t,
yUg,
by means of the relation derived from the equality of presand obtain the value of a for plane surfiices in terms of From this, by differentiation, we may obtain directly //3, etc.
?^s(i)
the values of
Acd? Ad)?
,
etc., in
terms of
t,
/n.^,
//g, etc.
This
if
would
braic
l)e
But,
the
elimination oi
from the
all
finite
in
differential
dp/',
d^.
a
ol)tain
398
J.
W. Gibhs
differential equation
etc. in
^'2(1)5
^3(1)5
terms of
t, f4 ^,
may
with (514).*
* If liquid mercury meets the mixed vapors of water and mercury in a plane surface,
and we use
//,
and
/i.^
tively,
e.,
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 r2(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 watervapor 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
da
supposed
dition
may
be regarded as
fulfilled in
law of Daiton
we
shall
= 72
df^'i,
where
2^2
denotes the part of the pressure in the vapor due to the watervapor, and
Hence we obtain
da
For temperatures below 100 centigrade, this will certainly be accurate, since the presmay be neglected.
The value of a forp^^O and the temperature of 20 centigrade must be nearly the same as the superficial tension of mercury in contact with air, or 55. CS grammes per The value of a at the linear metre according to Quincke (Pogg. Ann., Bd. 139, p. 27).
same temperature, when the condensed water begins
in
to
sum
mercury
in contact
own
vapor.
+ 8.25,
or 50.8.{
its
grammes per
metre,
we
condensed in mass),
metre.
As p.^, therefore, grammes per square metre (when water begins to be a diminishes from about 55.03 to about 50.83 grammes per linear
vapor and water with
air.
were
determined by experiment, we could easily form an approximate estimate of the values of the superficial density Fgd) for different pressures less than that of saturated vapor.
It
does not by any means depend upon inappreciable differences of superficial tension. The greatest difficulty in the determination would doubtless be that of distinguishing
between the diminution of superficial tension due substances which might accidentally be present.
sideraVile practical
to the
J.
W. Gibhs
;J99
may
them
If
we make
= y^'
=y^"
=.
df.1^ di^t^
dp"
4 y^"
da
I\
d/.t^
1\
/"g
if
dp =:dpj\
{,'
yr")<h',
{y2
r,")<^M2
^.
and
da
That
is,
= r, ,
,<,/;), /4, etc.
~,, du^
I\ du.
Yi
distance
be
7 Yi
Yi
j.
represents the
tween the surface of tension and that dividing surface whicli would make T^j zz the second number of the last equation is therefore
;
equivalent to
If
j'^^d)
any component substance has the same density in the two homogeneous masses separated by a plane surface of discontinuity, the value of the superficial density for that component is inde})endent
of
we may
Thus
when
second
member
i(,
will reduce to
/"g
It
is
make jo' ji^", /^3, /<^, etc. constant making t, /<j, /.<3, /.(^, etc. constant.
Substantially the same
is
in this case
equivalent to
same density
in the
two
homogeneous masses.*
* With respect to questions which concern only the form of surfaces of discontinuity,
such precision as
is
we have employed
in
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
we
51
July, 1877.
400
J.
W. Gibhs
Kqii'dibrlum of Heterogeneous
the Stability
Suhstcmces.
Concendng
of Surfaces of Discontinuity.
We
homogeposition
while
its
to
masses are very large, and thoroughly stable with respect to the possible formation of any different homogeneous masses out of their
is
plane and
Let us distinguish the quantities which relate to the actual components of one or both of the homogeneous masses by the suffixes
at the surface of discontinuity
components which are found only suffixes ,,,;,, 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
, J, etc.,
relate to
by the
surface of tension.
its
changed
state
supposed to be
equilibrium
still
uniform
in nature,
as
may
subsist
in
between the
given
modynamic
size to
state.
The remainder
and on accoxmt of
greater
be infinitely less altered in its nature than the first part. Let As^ denote the increment of the superficial energy of this first part,
Arf^
Ami,
^^iif
ftc, Ainfj,
Amf
etc.,
the increments of
its superficial
determinate values to the superficial densities of energy, entropy, and the component
substances,
which
quantities, as
between the tension of a surface of discontinuity, and the composition of the masses
which
it
separates.
cr
The product
ture
regarded as the available energy due to the surface in a system in which the tempera
//,, /i 2, etc.
or
when
the system
is
subject to gravity
are
The value of a, as well as that of s, is sensibly indewhich we may assign to the dividing surface (so long
,
the suiwrficial
used
in
this paper,
lilce
entropy and of
tlie
dividing surface.
J.
W. Gihbs
Equilibrium of Heterogeneous
jSub.stances.
401
entropy and of the quantities of the components which we regard The increments of entropy and of the as beh)nging to the surface. various components which tlie rest of the system receive will be
expressed
by
^nr:,
Anvi,,
etc.,
^ /Itf,
tAif"
Jw.!;
will
//,,
^'*
etc.,
//
Anil
//,,
Jnv),
etc.
/<!,
fi,,
Anif,
etc.
Hence the
total increment of
energy
in
At^
Aif
ii
If the
Ami // Anr; ^
is
etc.
ii/,Ani.l
(516)
etc.
necessarily
positive,
iart
for
finite
of the film
which Aa^,
etc.
relate,* the
nature of the
its })ositi()n.
if
we
write
etc.
De^,
JJif^,
Dntl,
Bin^,,
etc.,
i>m^
Bn^,
any element of the surface of discontinuity, we have from the supposition just made
for the energy, etc. of
ABe^ 
ADif
//
A Due: 
,j,
ADmf,
etc.
//,,
AJJnil
;/;,
ADmf
etc.
>
(51V)
=
//
0,
A/Dmt=0,
/,,
etc.,
we have
z//7>6^
 A/Bift
A/Ihn^,
A/Bml 
etc.
>
0.
(518)
Now AfDif is the inciement of the entropy of the whole siirface, and A f Dff is therefore the increment of the entropy of the two homogeneous masses. Tn like manner, AfDm\^ AfDrnl, etc.
are the increments of the quantities of the components in these masses.
The expression
 AfDif t
//
AfBml 
;/
AfBml film,
etc.
the sign
A must be
orders.
zero.
Otherwise, by equation (501), the above expression would have the value
402
J. TT^
Gihhs
of
denotes tlierefore, according to equation (12), tlie increment of energy tlie two homogeneous masses, and since A/De'^ denotes the
increment of energy of the surface, the above condition expresses that the increment of the total energy of tlie system is positive.
That we have only consideied the possible formation of such tilms as are caj^able of existing in equilibrium between the given homogeneous
masses can not invalidate the conclusion
in
the film, for in considering whether any state of the system will have
less
state,
we need only
least energy,
which
is
infini
tesimal change in the nature of the part of the film to which the
symbols
relate,
the film
is
obviously unstable.
finite
and not
film,
the film
in
practically unstable*
e.,
if
made
increase.
But
it
might be necessary that the initial disturbance finite magnitude in respect to the extent of
occurs
;
for
we cannot
parts.
dynamic
On
changes which we have been considering are such that every part
of the film
remains
;
in
on each side
and
if
by
may
perhaps be capable
by an
infinitesimal
same
condition.
We
change which does not satisfy the must therefore leave it undetermined whether
is
practically unstable,
is
or
is
not
unstable
in
which we need not distinguish between finite and infinitesimal changes. To determine whether the expression (516) is capable of a
negative value,
capable.
we need only
it
it
is
Let us write
in the fuller
form
/.;
(mf  mf
,il
{mr  mT] 
etc.,
^^^^
where the single and double accents distinguish the quantities which
*
With respect
term
is
used,
J.
W. Gibhs
403
accents denoting those quantities which have the same value in both
states.
The
when
guished by double accents are alone considered variable, and the area
of the surface
is
by
(//r
i.i;)
dmr + etc.
we must have
=1
0,
0.
To make
unless unless
mf
wif"
=:
//;' ,
by equation
e.,
(}"swhich
will
ff's,
g'
(520)
is
positive or negative.
That is, if the tension of the film is less than that of any other film which can exist between the same homogeneous masses (which has therefore the same values of t, yu yu^ etc.), and which moreover has etc., so far as it contains the the same values of the potentials jj^ substances to which these relate, then tlie first film will be stable. But the film will be practically unstable, if any other such film has a [Comj^are the expression (141), by which the practical less tension. stability of homogeneous masses is tested.]
,
, ,
/j,, ,
It is,
we have by
and by
e"
m/'
I,
etc. = 0,
/J
m,"
etc.
=.
0,
if
we denote by
f,
?/,
V,
m,
m^,
etc.,
m,
m,,,
etc.,
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
404
s
J.
W. Gihhs
1 1/ \
pv
//
/<,,
7n,,
etc.
/j
>//,,
jj,,
mi
etc.
=:
<J s.
Now
this
if
the value of
will
is
first
member
of
equation
decrease
may
therefore be
two kinds
will
of
There
given value of
as the strata
is
applicable,
e.,
so long
have the properties of similar bodies in mass. But it may easily be shown (as in a similar case on pages 131, 132) that
of
P,
Ma,
/'/,,
etc.,
//,
//,,
etc.
by the
surface of discon
question,
f,
7/,
etc.,
?^,
?/,
etc.
may
volume
will
?',
the
first
member
negative value, and must therefore have a least possible value, which
be negative,
if
any value
f,
is
negative, that
etc.
is,
if o" is
negative.
least value
?/,
which
With
two homogeneous masses and the surface of discontinuity with the negative tension is by (53) (see also page 133) at least practically
unstable,
if
is
it
can
of the potentials.
if all
the component
Therefore, in a
form
s{G"
a')
/'//)
etc.
when the
quantiis
infinitely little
J.
W. Gihbs
405
accents relate.
so too,
is
But if one film is stable, the other will in general be and the distinction between the films with respect to stability If all films for all of importance only at the limits of stability.
ja^^
jj,,,
values of
it is
evident
when
the quantities
same
limits.
by any two infinitesimally difierent films within the For such collective determinations of stability the
condition
may
be written
sJff^mfj
or
z/ (7
Aj.iy
j.i,j
nt^,zij.i,^
jj,,
etc.
^
etc.
0,
< r; J
r,,
(521)
On
comparison of this formula with (508), it apj)ears that witliin the and higher difierential coeflicients of the
which are found only at the surface of discontinuity (the potentials for the substances found in the homogeneous masses and the temperature being regarded as constant) satisfy the conditions which would
make
the
the tension a
maximum
if
were
is
In the foregoing discussion of stability, the surface of discontinuity supposed plane. In this case, as the tension is supposed })Ositive,
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
sj)herica]
and uniform
throughout.
In order that the equilibrium of a spherical mass entirely surrounded 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
may
be written
2G=r{2^'.p"\
(522)
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
instability,
it is
necessary that
the equation
2do={p' p")dr
shall
rdp'
the relations between da., dp\ and dr are determined from the fundamental equations on the sup])osition that
satisfied,
be
when
406
J.
TK Glbbs
remain
satistied.
Moreover,
if
i.
e.,
if
necessary to
is
stable.
But
if
'%>'%
the equilibrium
ijs
"'^^'^
when
<^^*)
unstable.
dp
is
therecall
In general, therefore,
we may
(523) the condition of stability. When the interior mass and the surface of discontinuity are formed
entirely of substances
and a cannot vary and condition (524) being satisfied the equilibrium is unstable. But if either the interior homogeneous mass or the surface of discontinuity 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\^ 7",,
and
yUj,
or,
by
(98)
and
(508),
(r;//
r,)'^'
</'/.
(526)
In these equations and in all which follow in the discussion of this case, the temperature and the potentials //g, /'s, etc. are to be
regarded as constant.
But
J.
W. Glhhs
407
which represents the total quantity of the component suffix, must be constant. It is evidently equal to
I nr^
by the
y ^'
4 7tr~ r^.
Dividing by
4;r
and
diiFerentiating,
we obtain
r^
dr\i
dy ^
r^
dl\
0,
//,,
(.,V
(627)
By means
the form
brought to
If
we
eliminate r
by equation
(522),
we have
\P'P"^ ^)
3 ( jo'
>i
1
.529)
jt>") fZ//
"*"
J
2
,
o djJ.
If
/:>'
and
ff
are
known
in
terms of
t,
//j
yUg? ^^.c,
we may express
the
first
member
p".
This
the values of
If
any given state of the external mass, which will make the equilibrium stable or unstable. the component to which y^' and F^ relate is found only at the
//,
(I If
^
Smce
y
1
dT,
>
5
2
(^^^)
=
'
o"
we may
also write
r.
dff
d log
Again,
if
3 y,'^
du,
Since
y'
also write
= ^,
djji^
we may
_y,'_d
Trans. Conn. Acad., Vol.
III.
^gjy_y')
d\ogy^
52
p'p" dy"^^?,'
^3
^^'^'^^
Nov., 1877.
408
J.
W. Gibbs
is
When
(533)
special conditions (531) and 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 discontinIn this case, uity, which are not components of the enveloping mass. we have instead of (526) a condition of the form
Fj, unless
very small.
The two
(*
r/
+ 2 I\
1^'
(r
r, '+27
,) '^^
etc.
<y'  p\
(534)
from which 
',
y^, etc.
may
1\
s,
ra' ^'
+ ^2
^S
etc.
must be
constant.
may
Two
different
homogeneous
orifice, their
by
diaphragm hav
ing a circular
to
(522)
may
dr
in this case
be
d(p'
;/)
da
,,.
/..\
where the quantities relating to the concave sion are distinguished by a single accent.
If
if
all
jf
and a
will
The
surface of tension
To
if
we denote by x
the radius of the
is
the part of
the axis of the circular orifice intercepted between the center of the
orifice
orifice,
and
shall
by
when
plane,
we
and
v'
{r
x)
7t x"^.
J.
W. Gibbs
409
By
and
diiierentiation
we
x)
clx
\
\
xdr
rX
=.
0,
civ' z=. 71
x^ dr
{2 TT
x~) dx
whence
(r
x) dv'
n r x^
dr.
(536)
By means
may be reduced
,
to the form
dp'
dp"
2da
(P
 P)
r
it
x
r^ x?
all
i2
^,
'
(537) ^
now suppose
//,,
cept one,
when one of
the
the
homogeneous masses
is
components of the system except one, or when both these masses are very large and there is a single substance at the surface
of discontinuity which
is
also
is
when
re
exposed
But
constant
y^'v'
y^" v"
I\s
by the
suffix)
component
specified
must be
therefore, since
dv"
z=z
dv\
and
ds
2 =dv',
By
dfx^
d}.i^
d}x^
is
When
component of
s
j
either
and
'
may
generally
be neglected.
When
it is
Ki
dy =
dy z
may
we must not
apply the formula to cases in which the substance spreads over the diaphragm separating the homogeneous masses.
410
Substances.
equilibrium,
a condition
result,
any to the
when that
which
But problems
require a
Let
it
system
in a
surfaces of tension
It is
supposed that
masses are
satisfied, as well
surfaces of discontinuity
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
difficulty.
The question
is
to
be determined by
is in
question.
of the system are not in general states of equilibrium, and the rela
them.
by the fundamental equations may not hold More than this, if we attempt to describe a varied
equilibrium, they
may
fail
any
state of
the system.
masses are
is
entirely determined
but
if
the phases
do not
face of discontinuity
we have employed
For
we cannot
tinuity
by assigning
to
it
It
would be
J.
W. Gihhs
41
necessary to give the law by which the temperature passes over from
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
in
different in the
two phases
in
unknown
to us,
is
entirely determined
is
by
we have occasion
surfaces of discontinuity.
It
may be
obsei'ved that
we have
which only
initial
state
is
neces
Such equations
may be regarded
as estab
rium.
when we
dis
Such equa
We
is
in question,
it
will
attri
We
which we may
is
call the
from the
(500)
may
we must decide whether we are to examine the question of stability under the condition of a constant
Before proceeding farther,
external temperature, or under the condition of no transmission of
412
<J.
'tV.
Glhhs
be conand that neither matter nor heat can be transmitted through it. Other cases may easily be reduced to this, or treated in a manner entirely
inflnences
we
is
fixed,
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 belonging to the vai'ied state just mentioned, there
must be a
state
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 difter in respect to those states which
satisfy all the conditions of equilibrium for each surface of discontin
That is, the imaginary system has a state, differing infinitely 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 This may be described, the real system will also have such a state.
uity.
little
shown by
imaginary system
The
surface of dis
will be the
We
which the entropy, quantities of components, and exterior same as in the given state, but the energy less. may therefore determine whether the given system is or is not
unstable,
to the
imaginary system.
If the
stable.
system
is
either neutral or
is
the case
by
refei'ence to the
this determination
depends
J.
W. Gihhs
413
systems do not
diifer.
by
(3)(7) to the
imaginary system.
as follows:
The
all
result Avhich
in
the small parts taken separately are stable, the criteria of stable,
neutral,
under constraint to satisfy the conditions of equilibrium relating to temperature and the potentials, and as satisfying the relations expressed by the fundamental equations for masses and surfaces, even
when the
(500)]
It
is
to
pressui'e
[equation
not satisfied.
tions (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
have as small an area as it can receive by any slight variations under the same limitations and that in seeking the remaining conditions of
;
when these are satisfied, it is only necessary to consider such varied surfaces of tension as have similar
stable or neutral equilibrium,
the method which has been desci'ibed by applyproblem but slightly different from one already (pp. 408, 409) discussed by a different method. It is required to determine the conditions of stability for a system in equilibrium, consisting of two diiferent 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.
We may illustrate
it
ing
to a
condition of
we need only consider those varied surfaces of tension which satisfy the same condition. may therefore regard the surface of tension as deterarea for the surface of tension,
is
We
v',
But the 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 variableand therefore, since the entropy and the quantities of the components are constant, the state of the system must be completely determined
state of the system
mined by
by
We may
therefore reoard
414
all
J.
W. Gibhs
and the
condition of stability
may be
^
,
written
(Z2f
de
j,av 4 
dv
TTo dv dv^
+ etc. ^ > 0,
*
'
where
di
is
that
(541)
,,^.>0.
Now
if
we
write
f',
f", f^
and (501), since the total entropy and the total quantities of the several components are constant,
the surface,
(86)
we have by
d^
or, since
jo'
dv'
p" dv"
ds ^_
ds,
de _,= _y+,/ +
(542)
Hence,
d'^e
dv^^
_ _ dp'
d^s
dv'^
dp"
da
ds
d^s
v5
'^)
stability
may
dj)'
be written
dp"
dv'
da
ds
^
dv'
dv' dv''
If
we now
by supposing,
on page 409, that we may disregard the variations of the temperature and of all the potentials except one, the condition will reduce to
d^s ^
/
,
T^
ds \ du,
''<r.>('''
<"='
is
The
y.'v'
^y."^"
r\s.
Making
this constant,
."
we have
(./
r.
,)*/+(.
is
g + ^ +
+
,
/^)...=o.,o)
The condition
of equilibrium
d^s
{y^'^'^"
V 4^ClfX^
+ ^^%)'
,
"^dv'^^
,dr,'
dr/' V f~ +
ClfX^
dry
s
^^^'^
^
(IfX^
J.
W. Gihhs
415
where ^= and ^ are to be detertnined fioni tlie form of the surface civ dv of tension by purely geometrical considerations, and the other differential 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
, ,
when we can
treat
may
F'or if
we
write
2 As for
may
be
sum
written
2/le
f
:^At^
>
0,
(548)
the total entropy and the total quantities of the several components
being constant.
The
z/ signifies,
higher orders.
stant, the same will be true of the pressures and surfacetensions, and
by
integration of
/ie
(Sti)
ol)tain for
any homogeneous
mass
and
J/;
p iv +
Am
\
//g ^'i^i
+ etc.,
etc.
for
Ajf
(7
As
{ //j
A7n\ f
//
Am.^ f
These equations
/ig, etc.
will
hold true of
finite differences,
when
<,
^, a, //,,
are constant,
ferences,
and will therefore hold true of infinitesimal difunder the same limitations, without neglect of the infinitesi
By
form
0,
0.
or
:^{pAv)
2{2jAv)
(549)
That
is,
the
the surfaces
by by the sum of the products of the areas of of discontinuity by their tensions must be a maximum.
III.
sum
This
is
Nov., 1877.
416
sioiis
J.
iSubstances.
are constant.
of interest, because
it is
always
tinuity.
by
tubes
and potentials. This may be done without introducing any new The condition (549) when movable surfaces of discontinuity. applied to the altered system is therefore the same as when applied But it is sufficient for the stability of the to the original system.
altered system,
its
and therefore sufficient for its stability if we diminish freedom by breaking the connection between the original system
parts,
and therefore
On
the PosslhlUty
of
the
Formation of a Fluid of
different
Phase
The study of
homogeneous
fluid
masses
some of them) and having the same temperature and the same
we must
first
of all inquire
is
how
far
our
method of treating
surfaces of discontinuity
applicable to cases in
which the radii of curvature of the surfaces are of insensible magniThat it should not be applied to such cases without limitation tude. is evident from the consideration that we have neglected the term i(Ci C^8{c C2) i" equation (494) on account of the magnitude
^
of the radii of curvature compaied with the thickness of the nonhomogeneous film. (See page 390). When, however, only spherical
masses are considered, this term will always disappear, since Cj and C2 will necessarily be equal. Ao^ain, the surfaces of discontinuity have been regarded as separat
homogeneous masses. But we may easily conceive that a globumass (surrounded by a large homogeneous mass of diflerent 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
ino
lar
vve
phase of matter in mass. This, however, will cause no difficulty, if reoard the phase of the interior mass as determined by the same
* See page 161, where the term stable
is
in a less
strict
J.
W. Gihbs
417
mass as in other cases. Beside the pliase of the exterior mass, there will always be another phase having the same temj^eratuie and potentials, but of the general nature of the small globule which is surrounded by that mass and in equililjrium
relations to the exterior
with
it.
This phase
is
sidered,
and
contact with
it
at a plane surface.
and perfectly capable of realizamass could exist in This is the phase which we are to
we
ing surface.*
With
this
fictitious
no ambiguity
in
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
the symbols which
The dividing surface, which any material modification. **, if, in\, m, etc., is as in other cases to be placed so as to make the term ^(C^ 4 6\)^(Cj fCg) in equation (494) It has been shown vanish, i. e., so as to make equation (497) valid.
require
it
nonhomogeneous film But of curvature which are large compared with its thickness. 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
I'adii
it
is
natural application.
globule in
equilibrium with
surrounding
homogeneous
and contain
may
and
G from equations
(497),
(500)
we
2
0'
may
be written
{p'
p")r,
[m.^],
(550)
If
we
write
[f],
[//],
[m^],
etc.
for the
* For example, in applying our formulae to a microscopic globule of water in we should understand, not the
actual density or pressure at the center of the globule, but the density of liquid water
(in kirge quantities)
which has
tlie
418
J.
W. Gibhs
excess of the total energy, entropy, etc. in and about the globuhir
same space
if it
were uniformly
with matter of the phase of the exterior mass, we shall have necessarily with reference to the whole dividing surface
,s
^,]
_
^''
' (,^.'
,/),
Yi")^
^^1
[''^il
iVi
^,
(,^^/
^''
,^^,.)^
iVi
r/)^
etc.,
where
y^',
y y"
etc.
We may
aS
= [e] 
V' (fy'
6y")
t [/;]
V' (//y'
//y")
^i,[m,'\\fi,v'{y,'y,")ti2[m^]+^i.,v'{y.,y.,")^^tc.
(551)
But by
(93),
p'
p"
ri"+
/V2
^2" +
etc.
for brevity
[f]
W=
(It will
t [;/]
//,
[m,]
1.1,
[m.^
etc.
(552)
is entirely determined by be observed that the value of and that the notion of considered, system physical the nature of the
way
enter into
its definition.)
We
shall then
have
a
or, substituting for s
W+
v'
v' ip'
2)"),
r,
(553)
and
r^
a z=
W+
{jy'
irrr^
(^V
p"),
(554)
and eliminating
ff
by
(550),
^rrr^
p")
= W,
(555)
If
we
eliminate r instead
ff,
we have
Now, if we first suppose the difference of the pressures in the homogeneous masses to be very small, so that the surface of discontinuity is nearly plane, since without any important loss of generality
J. AV.
Gihhs
Equ'dibruim of Heterogeneous
o' is
/Substances.
419
the
not positive
when
p'=.p",
stable in
regard to position, as
certainly
is,
in
fulfilled
with respect to
perimeter), we see by (550) that the presmust be the greater; i. e., we may regard
}>'
p\
and r
as all positive.
By
is
will
also
be positive.
But
it is
TF. that
any possible
become
and p'^zp".
from very small values, W, r, and o' have single, real, and positive values imtil they simultaneously reach the value zero. Within this
limit,
our method
it
is
evidently
applicable
beyond
this
limit,
if
such exist,
equaiions.
will
radius of the
But it must be remembered that the vanishing of the somewhat arbitrarily determined dioiding surface may
however,
come
insensible in
heterogeneous globule
initially the
in
For
this
work
is
is
formed without change of the entropy or volume of the whole system or of the quantities of the several components. Now [//], [^/^,], [^ig],
etc.
denote the increments of entropy and of the components in the is formed. Hence these quantities witli 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),
all
the globule
is
formed.
But
[f]
Therefore, by
W denotes
the total
re
increment of energy
in
these considerations
with respect to the stability of the homogeneous mass of the pressure p" (supposed less than ^>', the pressure belonging to a difi^erent phase of the same temperature and
jiotentials)
420
J.
W.
(iibbs
Within those
limits within
W,
the
work required
which would be
Nor can
size
surrounding mass,
of that to which
relates.
size
(page 406) been shown to be unstable, and with the least excess in
size,
We may
relates.
value of
is
given
in
funda
mental equations which give o', ^j*', and jt>" in terms of the temperature and the potentials were known, we might regard the stability
(
TF) as
that
known in terms of the same variables. is infinite. when p'=zp" the value of
It will
be observed
increases
If p'
p"
without greater changes of the phases than are necessary for such will vary at first very nearly inversely as the square of increase,
p'
p\
\i
p'^p" continues
to increase,
it
may
TFreachcs the value zero; but until this occurs the phase is certainly Another kind stable with respect to the kind of change considered.
of change
is
is
may
be great
in respect to continuous changes of phase has already been discussed These limits depend (see page 162), and its limits determined.
entirely upon the fundamental equation of the
which the
in
stability is in question.
chanoes here considered, which are initially small in extent but great
degree,
it
how we
with the same precision. But it is safe to say that if there is such a This limit it must be at or beyond the limit at which o' vanishes. equation of fundamental the by the entirely determined latter limit is stability the is of which phase the between discontinuity surface of is in question. formation possible which the of that in question and
We have
when
o'
ing surface
W vanish
with
it.
If the fault in
(it
the
at the
same time,
evidently
J.
W. Gihbs
421
limit.
But
if
vanish with
a and W,
appears
the
why
this
although
amount
work necessary
is
is infinitesi
mal, this
not enough to
is
therefore that TF
It
must be remembered
fundamental
is
in the
phase extends
in
Yet the foregoing discussion yields It has been shown that the real geneial beyond that limit (discussed
on pages 160, 161), which may be called the limit of practical stability, at which the phase can exist in contact with another at a plane
surface,
stability in such cases as
and a formula has been deduced to express the degree of measured by the amount of work necessary
when supposed
to extend indefi
would accommodate
By
may
ffs
be written
v',
Wz=z
 (y  p")
(559)
we
work
W consists of
tw^o parts, of
which one
is
always
positive,
and
is
and the area of the surface of tension, and the other is always negative, and is numerically equal to the product of the diiFerence of prespart as expressing the
by the volume of the interior mass. We may regard the first work spent in forming the surface of tension, and the second part the work gained in forming the interior mass.*
sure
* To make the
ph}'sical significance of the
above more
clear,
two processes
initially in
to be
performed separately
in the following
manner.
pose a large mass of the same phase as that which has the volume
the interior of the other.
to exist
Of course,
it
must be surrounded by
a resistino
We
that within.
We may
allow the
422
J. VT. Glbhfi
we
neglect
its sign,
is
first,
v'^r^^'s.
We
{p'
may
v'.
therefore write
(560)
W ^as=h^
On
the Possible
 p")
Formation
a.
Homo
either.
Let A, B, and
at plane surfaces.
diffei'cnt,
he three
The components of
and
B may
but
C must have no
or B.
and B to be separated
will
by a very
This sheet
not necessarily
zero.
principal curvatures
must be
We
may
and
thickness
its radii
comparison with
The value of
if wt"
be Cac+o'bc,
tensions of
tlie
and C, and B and C, respectively. from evident mechanical considerations, but appears only not This verified by equations easily be also (502) and (93), the first of may
surfaces of contact of the phases
which
may
a.
not be affected
the
superficial area.
If this
be done
phase
mass within will remain constant. (See page 139.) A homogeneous mass of the volume v' and of the desired phase has thus been produced, and the work gained
is
is
volume
//
of the
and
to the edge of the orifice, but not elsewhere to the outside surface of the envelop.
in
^{'p' p")v'
and the
will be resisted
by the
capillary tension.
J.
W. Gibbs
423
limit
is
Now
if
o'ac+ ^bc
and B, such a
We
cannot sup
between
pose that 0'ab^<5'ac+ <^BCi for this would make the ordinary surface A and B unstable and difficult to realize. If o'ab=o"'ac+ Cbc,
we may assume,
relation
is
and
of the kind
which
still
we have
described.
Let us
now
and
to vary, so as
to
C determined by
become
less
and B. A A and B will be entirely stable with respect to the formation of any phase like C. (The case is not quite identical with that considered on page 161, since the system in question contains two different phases, but the principles involved are
of
and
shall
With
direction
and
in
the opposite
we must
consider
two
cases separately.
It will
be convento
make jii9A=Jt)B=^:>c5
jOa=/*b,
it
will not
and
so that
and Pc^pA,
foi"
by
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.
we can vary the temperature and potentials and^c^i^A, and it will not be possible for a sheet of the phase of C to form irnmediately, i. e., while the pressure of C is sensibly equal to that of A and B for mechanical work equal to
But
if o'ab<^<5'ac+<5'bc5
so that ^;<A=i^B5
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.
<5'ac+<5'bc o'ab per unit of surface
III.
54
Nov., 1877.
424
J.
W. Gibbs
Eq^dUhrinrn of Heterogeneous
system
in
Substances.
The
less
stability of the
must therefore
and B.
We
arrive at the
when the
must
it
make
become unstable,*
In the preceding paragraph
of phases
and
is
stable
it is shown that the surface of contact under certain circumstances, with respect
To complete the
for
it is
in lentiform masses.
if
This
is
manner,
antl
at
all,
likely to
be
C would
evidently be unstable
when
o'ab<^<3'ac+
o'bc,
masses.
It will
be convenient to consider
in
and
which
sur
meet
plane surface.
Let
figiire
10 represent a section
of such a system
faces, the
mass of phase
lying on the
left
of
D E H' F G,
Let
on the right of
D E H" F G.
L Let the radii of EH'F and E H" F be denoted by r', r", and the segments I H', I H" by x\ x". Also let I E, the radius of the circle in which the spherBy a suitable ical surfaces intersect, V)e denoted by K.
and
in
Fig.
10.
we
may
Cac
,
x'
r"
ffhc
h
we
J =
x"
considering
,
Gak,
(561)
* It
is
are
now
is
discussion referred
which
any
different
homogeneous masses.
(520)
is
perfectly valid in this case with respect to the possible formation of a thin
<
',
we have
seen,
may
J.
W. GihhsEquiUhrhim. of Heterogeneous
components parallel
(T^b
Substances.
425
which
(Tac
to
EF
of the tension
and
If
we denote by
tlie
amount of work which must be expended in order to form such ;i lentiform mass as we are considering between masses of indefinite extent having the phases A and B, we may write
TF
J/
iV,
(562)
where denotes the work expended in replacing the surface between A and B by the surfaces between A and C and B and C, and A^ denotes the work gained in replacing the masses of phases A and B by the mass of phase C. Then
31=
where and
6'ac, Sge,
(T AC
Sac
'S'bc^bc
^ab ab,
(568)
;
Sab
]V=
Pn),
(564)
where F' and V" denote the >'olumes of the masses of the phases A and B which are replaced. Now by (500),
2 <5^AC Pc~Pa= ,
^BC pcps^'
'^
(565)
We
F' r= f
;r
r'2 x'
c"
^
^
tt TT
R''
(r'
 x),
(566)
x!').
V" =
%7i r"2
7^2 (r"
By
substitution
we
7t
obtain
N= I
and by
(561),
o'ac r' x!
\7i
^"
R^
Oac
^ r
ff^,
+t
;r oBc /"
^'inR^
tt (Tbc
''~^.
(567)
N=
Since
2
n
X
+
'^
r"
x!'
%7T R^
TT
(Tab.
(568)
7T r'
Sac,
T?"
r" x"
Ssc,
R^
Sab,
we may
write
^= I
(o'ac *^ac
O'bc 6'bc
O'ab Sab).
(569)
is
the same as
We
have therefore
W=
This value
is
ij
(oAc Sac
O'bc ^bc
^ab 5ab).
(570)
positive so long as
42(3
J. ^V.
Gihhs
E(j[vilihritim
^s^c
of Heterogeneous Substances.
since
>
s^b,
and
6^
>
6\vb.
But
at the limit,
when
G.KC
O'Br
Cab,
we
see
by
(561) that
<*AC ^^^
^ABj
anCl
Sbc
0,
i'*AB?
and therefore
It
TF
circle in
intersect,
the
by the
We
ble magnitude.
We may
will not be
conclude that after we pass the limit at which p^ becomes jOr (supposed equal) lentiform masses of phase C
until either o'ab=o'ac4o'bc, or p^,
formed
jOa
becomes so is one
Hence, no
ing values of
PcPh
is
by equation
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
disregarded when the lentiform mass
is
of sufficiently small.
The
is
easily
proved
affords a kind of measuie of to be unstable, so that the quantity contact of the phases A and B.* surfaces of plane the stability of
*
If
we
(in
phases
same
point,
positions of
and allow ourselves, for brevity, to speak of the phases as having the the points by which they are represented, we may say that three coex
where three
all
series of
fluid,
meet or
or
when
may be
disregarded,
to be distinguished.
phases
all
intersect,
two others, or one of the series terminates where the two others intersum The series this is where one surface tension is equal to the sum of the others. gect of coexistent phases will be represented by lines or surfaces, according as the phases
of the
this is
when each
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.
J.
W. Gibbs
42*7
have moderately
C may
be
in
equilibrium
where
Cj
and
C2
film,
the
Eliminating
c^\C2,
we have
Cbc {Pk
 Pc) =
(Jkc
{Pc
 Pb\
It is
pc has a value greater than that determined by mass; if jt>c has a value, such a film will tend to diminish. Hence, when
if
evident that
Obc
(^ac
the phases
Again,
if
between
and B have a stable surface of contact. more than one kind of surface of discontinuity is possible and B, for any given values of the temperature and potenbe impossible for that having the greater tension to
dis
tials, it will
con
and consequently o'ac+o'bc is one value of the tension for the surface between A and B, it is impossible that the ordinary tension
of the surface
o'ab
this.
If (J'ab=<5'ac+0'bc5
when equation
the phase
(571)
we may presume
make p^
it
second number of (571) cannot be brought about at that surface, as would be prevented by the formation of a larger mass of the phase
C.
But
if
o'AB<C^Ac+crBc
when equation
mark the
between
finite
and B,
for the
428
J.
W. Gihbs
we
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
TF=
(Tac
'*>ac
G^c >%c
Cab ^ab
(573)
 Pc Vc + Pa T^a + Pb Fb,
where /Sac, i^bc denote the areas of the surfaces formed between A and C, and B and C, S^n the diminution of the area of the surface between A and B, F^ the volume formed of the phase C, and V^, Fg the diminution of the volumes of the phases A and B. Let us now suppose (Tac, O'bc, o'ab, Pa, Pb to remain constant and the external boundary of the surface between A and B to remain fixed, while pc
increases and the surfaces of tension receive such alterations as are
It
is
we may suppose
the changes
Then, regarding TF simply as an abbreviation for the second member of the preceding equation, we have
f^'^^'AB
Vcdpc.
(574)
requii'e that
C'bc
dS^c
Cab
^^'^ab
pcdVc^Pj,dVj,+pjidVB
Hence,
0.
(575)
dW=
Now
it
Vcdpc.
2^c
(576)
increases.
its
is
evident that
Vq.
will
diminish as
Let us
original
where
W'
1F"=0.
and Hence
W=
a negative quantity,
(577)
But
in the
is
positive.
But
work necessary
and B.
It is
J.
W. Gibbs
Equilibrium
We
of Heterogeneous Substances.
429
that Pc Phi PcP^ of the lentiform mass are of dimensions must not be so great that the
as in the less general case already discussed,
insensible magnitude.
It
may
of
these differences
may
and
for
In this case
we may
A mass of phase C which is which the three and B in virtue of a constraint applied to the line in 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 is positive by such an integrain equilibrium upon the surface between
tion as
we have used
before.
Substitution
adapted to the purposes of theoretical discussion, especially when the number of components is large or undetermined. But the experimental determination of the fundamental equations, or the application of any result indicated by theory to actiial cases, will be flicilitated
by the use
depend upon less complex considerations. The numerical value of a potential depends not oidy upon the system of units employed, but
upon the arbitrary constants involved in the definition of the energy and entroj^y of the substance to which the potential relates,
also
or, it
is
may
(See page 152.) measurement may give a certain vagueness to the idea of the potentials, and render the equations which involve them less fitted to
formed,
direct
Now
which are separated by any surface of discontinuity affords a relation between the pressure in that mass and the temperature and potentials.
We
aie
two
is
a gas
430
J.
TK Gibhs
mixture which
satisfies
may
be expressed
in
we may
eliminate as
By the many
simple gases
in
the gasmixture.
An
when the fundamental equations of the adjacent masses 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
relates, for
are
as an indispensable preliminary, or
however,
we cannot
by the
same
relations as
tensions, temperatures,
inquire, at least in the
and potentials. It will be interesting to more important cases, what relations may be
fundamental equations just
is
necessary
to regard
may be convenient
Now we
=.
7/s
dt
Fd/u
<^f
d{p'p")
=  [iH  yp,
Vv'
(5 V8)
differential coetticients of
with respect to
plane,
and
it
p".
is
evident that .
y
sion
r
make
the superficial
to a dividing
when the
./
W. Gihhs
431
latter surface is
by the
e.,
by
7/^,
on page 397.
two components, neither of which is co))fined to we may regard the. tension as a function of the temperature and the pressures in the two homogeneous masses. The values of the difterential coefficients of the tension with respect
there are
When
to these variables
may
be represented
in
a simple
form
if
we choose
This will
is
such substances for the components that in the particular state considered each mass shall consist of a single component.
not
and
coefficients.
We
then have
da =z
//s
dt
F^
dt
dfj^
F^^
dfj.^,
d2)'
7/v'
\
y'
dfj.^
dp"
= Vv" dt + y"
by
'
d/A^^
and
^^
and
to indi
component
sjiecified
specified
homogeneous masses
and
".
we
obtain
dff
= (?k ;
\
7v'
^ W) dt  ^ dp'  ^
y
J
djy".
(5 7 9)
We may
/)",
and write
(580)
da = 
(//,
^' ;a'
is
evident that
and
;'
represent the
dis
two
would make
F^
/"^^,
that 7
represents
two
surfaces, or the
ume due
cient
of dt
in a
(without
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 same phases but without any surface of discontinuity.
Trans. Conn. Acad., Vol.
III.
5.5
entropy
Nov.. ISTI.
432
J.
W. Gibhs
JEquilihrium of Heterogeneous
without any
Siibsta)ices.
(A mass thus
existingf
surfjice of discontinuity
must
of
The form
in
\dtjp
in
equation (580)
these quantities to the particular state of the system for which they
are to be determined, but not to
of the system.
state
For
ordinary components.
If
we eliminate
df/^
and
do'
and
g
dp
= = dp
df
~\
I\
d/.(
r]y'
dt
dt
//v"
+ r/ + ;//'
7
fZ/'i
f//<i
* If
we
set
and
in like
manner
)'
^'
(507),
(d)
we may
easily obtain,
by means
of equations (93)
and
Es
)f
Hs +
(T
 i9 F.
Vdp.
(e),
Now
equation (580)
may be
written
d(y=
K.di +
(e)
we
,
obtain
(/) of energy and
fact,
dE,
dHs i)d V.
The quantities Ej and Hs might be called the superficial densities entropy quite as properly as those which we denote by e^ and tj^. In
composition of both of the homogeneous masses
is
when
the
and
H are much more simple in their definition than s and ??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
tlie
surface of tension or
surface.
But such
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
The object of 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.
strictly
adhered
to.
how
a different
J.
W. Gibhs
433
we
obtain
j^ = dt
Ji.
(J
{
^ dp,
.A.
(581)
where
A
= rt"r2'ri'r2",
;/v'
(582)
B=
c= i\
It will
Ki'
r^'
(583)
ir,"
r2')
^^2
(ri'
ri")
(584)
be observed that A vanishes when the composition of the two homogeneous masses is identical, while Ji and C do not, in general, and that the value of ,i is negative or positive according as the mass specified by contains the component specified by ^ in a greater or
'
less
become infinite when the diiFerence in the com(^] and of (^ di/p V^pjt 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 155 respecting coexistent 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
The same relations are indicated by the graphical of the phases. method represented in figure 6 on page 184.
With regard
shall
to gasmixtures
suppose that there is not more than one component in the liquid which does not appear in the gasmixture. 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 it
Let this be
if
such there
if
there
is
no such component,
We
may
temperature, and the several pressures of the simple gases in the gasmixture or all but one of these pressures. Now, if we eliminate
(?/<25 ^A'sj ^^^' fi'oni
the equations
434
J.
W. Gihbs
da
r2, o
f^/^2
+
Ks
^zi\^
^^/^3
^tc.,
dp 2
dp^
= ^V2 =
<^<^
+ K2 ^t^2l
+
^/^35
7/v3 ^^^
etc.,
where the
suffix
relates to the
to vanish,
surface
made
and y^, y<,, etc. denote the densities the gas mixture, and p^iPz) ^^c, ?/v2) '/vs,
gases,
we
obtain
?i''
da
= (//sd)
/;v2
~
'/V3
etc.
/
dt
AiA^dp,^^l^dp,etc.
/ 2
3
ff
(585)
This equation
respect to
t,
aftbids
wdth
p, p^, etc., which may be set equal to those obtained by differentiating the equation between these variables.
to the
Extension of a
The fundamental equation of a surface of discontinuity with one two component substances, beside its statical applications, is of use to determine the heat absorbed when the surface is extended
or
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 com
ponent vanishes. (See page 397.) If we suppose the area of the surface to be increased by unity without change of temperatui'e or
of the quantities of liquid and vapor, the entropy of the whole will
be increased by //s(j). Therefore, if we denote by Q the quantity of heat which must be added to satisfy the conditions, we shall have
<?
= ^%(,,,
d(J dff
(586)
^.
^
and by
(514),
*^
,
dt
d\ogt
It will be observed that the condition of constant quantities of liquid and vapor as determined by the dividing surface which we
ll;ie
total
volume
./.
W. Gibbs
if
435
Again,
the surface
the pressure in the liquid and vapor remains constant, the temperature will evidently be maintained constant
by condensation
of the
vapor.
If
surface formed, and by a/m' and //m" the entropies of the liquid and vapor per unit of mass, the condition of no addition of heat will
require that
^/('/m"Vm')
= %(,).
(588)
The
^mT
(589)
/(W'/mT
nal bodies
(590)
Hence, for the work done (per unit of surface formed) by the exter
shall
have
vm
and, by (514) and (131),
'/u
\/
y/
da
dt
dt
dp
dG dp
da d log p'
'
Let us
not
now
is
Since
we
can
make
by
will be best to
We
mass
face
shall
extended until
its
area
is
increased
by
keep the temperature constant, and the pressure of the homogeneous masses is also kept constant, the phase
at the surface so as to
added
by
/"
Their
respect
by
T'
'
?/v'
and
r ~
r/y",
436
ively.
J.
W. Gibbs
by
'/s
r p
Vv
r
//
'/v
is
equal to
have
\dt/p
difference
\d\ogtJp
this
'
We
between
In
is
these
The additional condition by which Q is determined may be most simply expressed by saying that the total volume must remain
constant.
considering
Again, the differential coefficient in (593) is defined by in the differential coefficient in (587) p ^9 as constant
;
is
necessary to
differ
it is
This
William Thomson, who first pointed out these relations.* The diminution of volume (per unit of surface formed)
be
y^r.
;/'
r. y"
/do
\dp '+7'=(i).
<^'
and the work done (per unit of surface formed) by the external bodies which maintain the pressure constant will be
W may
By
substitution in (593)
differential coefficients
by
(581),
we
obtain
vol. ix, p. 255, (June,
1858)
./
W. Gihbs
43V
W=pj.
Q
and TTare
(596)
where A, B^ and
(584).
infinite
(J
by (582)in general
It will
for the
which
the
differ infiuitesimally in
and
quantity A.
it
When
the
phases
are
absolutely identical in
composition,
is
by any supply
of heat.
For
the matter at the surface will not in general have the same composition as the
for the
increased surface
by the
fact that
The infinite values of Q and when the phases are nearly identical
is
W are
explained
in composition,
accompanied by the
is
necessary
to keep the
is
extended,
we
by the extension of
it
changes sign
i.
with y
^" y2'
'^Yi'y/
>
^^^
e.,
vanishes
when
the composition of
This
may be
ments on page
When
initially abso
either
is
two
is
will
perature
maximum
minimum
The
most
befoie
effect
easily verified
by experiment
is
adjacent masses.
complete equilibrium has been reestablished throughout the A fresh surface between coexistent phases may be
regarded in this connection as an extreme case of a recently extended When sufiicient time has elapsed after the extension of a surface.
surface
originally
in
equilibrium
between
coexistent
its
phases,
the
superficial
tension
will evidently
have sensibly
original value,
unless there are substances at the surface which are either not found
438
./
W. Gihhs
com
But a surface
only a single
different tension.
is
component substance,
When there
are
of which
is
confined to the
when the
is
surface
it;
is
exif
tended,
i.
e.,
to cool
but
the tension of any surface increases with the temperature, the effect
of extending the surface will be to raise
case,
it
its
temperature.
In either
will
effect of
face
is
effect.
must
in
it
desirable to notice.
is
When
the superficial
normal
it is
surface can be taken from the immediate vicinity of the surface with
But
if
same component
is
very small
in
each
mation or extension of the normal surface must come from a considerable distance.
Especially
if
we
ponding potential
in
the
make
J. TF. Gihhs
439
and contraction decrease of the tension. It would evidently be inconsistent with stability that the opposite effects should be proincrease
duced.
may
be
When
is
normal value
will
the extension or contraction of the surface, the phenomenon resembling that of viscosity, except that the variations of tension arising
from variations
in
same
in all directions,
property of the surface really analogous to viscosity would be greatest in the direction of the
We may here
are very small,
homogene
When
surfacedensity
may have
a considerable positive
For the
by the
* When, however, homogeneous masses which have not coexistent phases are brought into contact, the superficial tension
may
The
room
is
will
dimin
we have chosen
incapable of resolution into other components which are independentlj' variable in the
homogeneous masses.
III.
56
Jan., 1878.
440
film.
J.
W. Gihhs
Each of these quantities is exceedingly small. The surfacewhen positive is of the same order of magnitude as the thickness of the nonhomogeneous film, but is not necessarily small comdensity
pared with other surfacedensities because the volumedensities of the same substance in the adjacent masses are small. Now the
potential of a substance which forms a very small part of a
homo(21*7).]
increased.
The
not
be
sensibly afiected.
[See (98).]
But the
and
will
be to diminish
[See (508).]
It
the tension
is
when
is
positive.
therefore
very
diminish the tension, but not possible that such a trace should greatly
increase
it.*
Impermeahle Vilms.
We have
The
all
is
a film of matter of
which
is
impermeable to some or
et
de Physique, Ser. 4,
appears that one per cent, of alcohol in water will diminish the
The experiments do
not extend to pure alcohol, but the difference of the tensions for mixtures of alcohol
and 20 per
cent,
water
is
cited),
of soap
by onehalf. These determinations, as well as those relating to alcohol and water, are made by the method of drops, the weight of the drops of different liquids (from the same pipette) bemg regarded as proportional to their superficial tensions. M. Athanase Dupre has determined the superficial tensions of solutions of soap by A statical method gives for one part of common soap in 5000 of different methods.
water a superficial tension about onehalf as great as for be measured on a
identical with that of pure water.
pui'e water,
but
if
the tension
is
same
solution)
sensibly
He
ficial
tension of the same solution as well as tlie 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 Chiinie et de Physiiiup, Ser. 4, vol. vii, p. 409, and vol. ix, ]). .'i79.)
J.
W. Gihbs
Equilibrhim
a film of
oil is
of Heterogeneous
Such
Stthstances.
441
may
be the case,
oil in
when
is
when
the film
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
In such cases,
there
is
regarded as an immaterial circumstance, so far as states of equilibrium are concerned, and our formula^ 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 difterent values on opposite sides of the film, and the case evidently
requires a modification of our usual method.
single consideration
If a certain
Avill
cases.
component which
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
must hold
stances.
true,
We
may be disregarded. All the general relations which would hold if they were really different submay therefore write //j for the potential of the comfilm,
and
ji^
same
if it
were a
different substance)
on the
ni\ for
above the quantity which would be on that side determined by the surface of
if
tension or otherwise)
m%
and dividing
smface.
tlie
On
we may
use 1\ and
I^
to denote
values of
siirface,
and
its
??ii',
m/, y ^^
and
densities in the
two homogeneous
masses.
a notation, which may be extended to cases in which 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 siibstances specified by the different suffixes
With such
is
the film
were
of
//j
all
really different.
//g,
The
2
be a function
and
components, and
tions
/',, i
/^j
^^'il^
^^^
equal to
its
differential coeffi
and
//g.
In a word,
all
may
442
J.
^Substances.
we remember always
according as
film.
it is
component
as a different substance
When
fixes
1
there
2
is
component
specified
and
in the film,)
we
shall
have
we wish
we may
set a. single
symbol
for /<i
and
//g in
form of the fundamental equation. Cases may occur of an impermeability which is not absolute, but which renders the transmission of
In such cases,
it
may be
may
latter
be
complete equilibrium.
by
T7ie
geneous Fluid Classes without neglect of the Influence of the Surfaces of Discontinuity or of Gravity.
Let us
now
deduce from it the conditions of internal equilibrium for such a sysIn accordance with the method which has been developed, the tem. intrinsic energy, (/. e., the part of the energy which is independent of
of gravity,) the entrojDy, 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 masses, and the other as belonging to these masses. The elements
etc.,
Ds
Dm\, Dm%,
Z^f^,
etc.,
to an element of
shall also
We
Ds and Dv
etc.,
resjiectively.
That
is,
Dm^
Din''
(597)
etc.
(598)
The
J.
W. Gihhs
parts,
443
into
two
one of which rehites to the elements Dm^, andthe The complete value of the variation of
d/Be"
in
(599)
ele
which g denotes the force of gravity, and ment above a fixed horizontal plane.
It will
height of the
of reversible variations.
be convenient to limit ourselves at first to the consideration This will exclude the formation of new
masses or surfaces.
We may
therefore regard
any infinitesimal
elements, and
several
in the
we then
by equations
we
shall
have
ft dBif
+./"//2
f^Uml
etc.
SBml + etc. 4 fg 6z Bm"+fg z dBm\ + /// z 8Bm\ + etc. + yV ^^ Dm^ + fg z dBni\ ^fg z 6Bra\ \ etc. =
0,
(600)
might seem that this condition, although always necessary for equilibrium, may not always be sufticient. It is evident, however, from the form of the condition, that it includes the
tion of the system, or reversil)le variation
in the
of
between the
difl:erent
(The necessary relations between the various quantities relating to each element of the masses and surfaces are expressed by the fundamental equation of the mass or surface concerned, or may be immediately derived from it. See pp. 140144 and 391393.)
The
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
444
tern.*
J.
W. Gihhs
we may
tions
ft
diJt,''
+ft dlJif =
0,
(601)
SlJs
+ fg
6z Bni'^fg 6z Bnv^
0,
(602)
+//', 6Dm\
\fgz6I)rn^\
+fgz6Dm\
(603)
+ etc. =
of condition
rately.
0.
in
in
any one of the three are evidently the other two, and the equations
The
This
maybe
(604)
fdJJif ifSBtf
0.
To
it is
= const.
is
the condition of
thermal
The
may
also be written
0.
(606)
if
be observt>d that
this condition
the
by heavy and
The
We
was
to
impermeable envelop.
to give the
influence of the
we wish
to limit ourselves at
we
shall give
up the
is
The
variations of the
it.
J. IV.
Gibhs
445
to the condi
and the
lines in
which
it,
are fixed.
any
the
and do not contain either 6p or Sff. Hence, in determining whether first member of the formula has the value zero for every possible
variation of the system of geometrical elements,
we may
assign to
the pressure jo, in each divided by the surfaces of tension, is a function of the coordinates which determine the position of the element Dv, to which the pressure relates. In the varied state
is
of the system, the element I)v will in general have a diflferent position. Let the variation 6}) be determined solely by the change in position
of the element
Dv.
This
may
in
i: which J^? are determined by the function mentioned ax ay dz and f^a', ^y, 6z by the variation of the position of the element Dv. Again, in the initial state of the system the tension o", in each of
,
'
is
a function of
which determine
the' position
varied state of the system, this element will in general have a diffeient position. The change of position may be resolved into a com
ponent lying
tion
in the surface
it.
6a be determined solely by the first of these components motion of Ds. This may be expressed by the equation
r>^
da
P.
da
446
J.
W. Gihhs
in wliieli
by
doo^
(5^Cc5j,
doo
the
With this understanding, which is also to apply to Sp and 6 when contained implicitly in any expression, w^e shall proceed to the
reduction of the condition (606).
With
divided
is
by
we may
write
/"p 6I)v
= Sfp Dv f dp Dv.
relates to the
But
it is
evident that
6j'pI)v=fp6NDs,
where the second integral
surfaces of discontinuity
bounding the volume considered, and 6]Sf denotes the normal component of the motion of an element of the surface, measured outward. Hence,
fp 6Dv
Since this equation
is
system
is
divided,
we may
fp
where
j)'
dJDv =f{p'^2^")
(609)
Ds, and
<^iV^is
and p" denote the pressures on opposite sides of the element measured toward the side specified by double accents.
/
and
(J
dfaJJs
where
c^
(positive,
when
which (JiVis measured,) Dlaw element of the perimeter of the surface, and 7' the component of the motion of this element which lies in the plane of tlie surface and is perpendicular to the perimeter, (positive,
(5^
when
it
Hence we have
for the
whole system
(6 JO)
fG6nsz=fa{c^
SNDsif2{(rST)Dlfd(rDs,
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
equilibrium
J.
W. Glhbs
447
+fg rSzUs
0.
y 6z \
d]))
Dv
+/:^{ffST)Diz=o.
(611)
Dl
shall vanish
Dv
shall vanish,
it is
necessary and
is
divided
by the
surfaces of tension,
shall
be a function of
z alone,
such that
(612)
't=gy.
dz
In oider that the coefficient of
Ds
P^'or
it is
it
movements of the
6 (1=0,
surface.
normal movements
we may
write
and
6z =z cos
3 dN,
vertical
The
first
y_y' =
The condition with
(T(..f.',)+^rcos5,
in
(613)
respect to tangential
in
^
In order that the
coefficient
= .,1.
of
(614)
in
Dl
(611)
shall
vanish,
we
must have,
any
:^{g6T)=0.
sions of the surfaces meeting in the line
(615)
This condition evidently expresses the same relations between the ten
per
which hold
in a plane.
for the
equilibrium
in
57
Jan., IS'ZS.
448
J.
W. GIbbs
The same
is
true
f6I>mlJ^fdDm\=0,
fdDml^fSI)ml
etc.
(It is
0,
t
)
(616)
i. e.,
that none can be formed out of others, and that the parts of the sys
tem
in
]ated
by parts
which any component actually occurs are not entirely sepain which it does not occur.) To satisfy the condition
.
it
is
necessary and
fx^\gz=z3I^,
etc.,
(71/ J,
\
)
(617)
J/gj 6tc. denoting constants,) shall each hold true in those parts
is
an actual component.
We
may
by parts
that the
is
viz.,
expression jA^gz must not have a less value in such parts of the
system than
component.
in a
contiguous part
in
is
an actual
From
we may
in
easily obtain
ff
are
known
terms of the
in
For
Cj
Cg
and second
differential coefficients of z
with respect
and p\ p'\ <J, and F in terms of the But the temperature is constant, and for we may substitute gz increased by a constant.
We
first
A'^ariables
and second
differential coefficients
But it will raiely be necessary to use so exact a method. Within moderate differences of level, we may regard ;/', y" and a as We may then integrate the equation [derived from (612)] constant.
coordinates.
,
d{p'.p")
*
= g{y"^y')dz,
homogeneous masses on page
It will
Tbe term
if
117,
and the
that
definition
may be extended
is
it
to surfaces of discontinuity.
be observed
sur
a substance
face of discontinuity,
well as
when
it
J.
W. Oibhs
449
= c/{y"/)z,
(018)
z to be measured from the horizontal plane for which p'=p". Substituting this value in (<>i:^), and neglecting the term containing
where
/ \
is
we have
c,+c,=^iz'Zl).,
(619)
where the
y"~}/'
is
coefficient of 2 is to be
regarded as constant.
very small.
We
If
may
we
sum
of the curvatures
we have
(/(y"7')
dz'^\ d'^z
.,
dz dz d'z
A
\
dz'^\
dx'^
d'z
dy^jdx'
dxdydxdy
\
) dy''
z.
(G20)
dx^
dy'^ I dy'
With regard
fraction,
it is
to the sign
to be observed that, if
we always
value of the root, the value of the whole fraction will be positive or
is turned upward or But we wish the value of the fraction to be positive when the greater concavity is turned toward the mass specified by a
downward.
single accent.
We
surface.
The
last
may be regarded
number
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).
* 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 197203. f
Compare page
206,
where
a similar
problem
is
450
J. TFT Cxlhhs
The mechanical
cial
importance, since
as satisfied in
any
are observable.
In such a mass,
when
mechanical equilibrium will take place very soon; thermal and chemical
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
will generally require less
;
time for
its
complete equilibrium
is.
reached.
When
components
may
for
mobility
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
(617),
since this
is
of
mechanical equilibrium
relating to temperature
connection
with
the
conditions
to be satisfied.
The necessary
of the surface.
mass containing
this
by
the surface, the potential for this component in the surface will of
by
tliat in
it
meets.
The
sist
which may be regarded as expressing the relations 'which must subbetween contiguous portions of a fluid system in a state of mechanical equilibrium, are serviceable in determining whether a But the mechanical theogiven system is or is not in such a state.
rems 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
by the application of
ordi
by
this equation.
will
temperature and
iiotciitials
arc
not affecteil by
tlie
surfaces of
J.
W. Gihhs
Equilihriiitii
(228)
<>f
Ileterogeiieous Siih.stances.
(2:U).] *
451
discontinuity.
[Compare
and
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 dirt'erence If the phases thi'oughout the of level of the two points considered. fluid system satisfy the general condition of practical stability for
phases existing in large masses
(viz.,
at any given point and the differences of (Compare page 210, whei'e the subject is treated without
regard to the influence of the surfaces of discontinuity.) Conditions of equilihriuni rdati^uj to irreversible changes.
conditions of equilibrium relating to the absorption
the system of substances which are not actual components of that part
ing to such changes, and are not always distinguishable from them.
They
We
have
mation of new
surface
fluid
fluid
and at the
a surface of discontinuity.
considered
surfaces.)
is
may
easily be
extended to curved
We shall
hereafter consider, in
and
])oints in
lines
to the
whole system.
Beside
the
permeable to
all
librium of the fluids relating to temperature and the potentials wUl not be affected.
(Compare page
extended
139.)
in the
above paragraph
may
be
to this case.
452
J.
W. Gihbs
tion of the
whole system or to considerable parts of it. To determine the quesstability of a giA^en fluid system under the influence of
gravity,
when
all
which relate to small parts of the sysuse the method desci'ibed on page 413, the demonstration of which (pages 411, 412) will not require any essential modification on account of gravity. When the variations of temperature and of the quantities 3/j, M, etc. [see (617)] involved in the changes considered are so small that they may be neglected, the condition of stability takes a very simple
as those conditions of stability
tem taken
separately,
we may
form, as
we have already
tem
uninfluenced by gravity.
We
total entropy
and the total quantities of the various components are and all variations vanish at the exterior of the system, unchanged,
moreover, the conditions of equilibrium relating to temof the masses and surfaces are to be
is
in which,
perature and the potentials are satisfied, and the relations expiessed
not one of
complete equilibrium.
tions
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 clE may be expanded like that of 6E in (699) and (600), and then reduced (since the values of t, /.t^+gz, ^t^' ^^'^ uniform throughout the system, and the total entropy h2~\'U
'^1
and
form
dE=i y> dl)v ^fg dz Bm^+fo' dDs {fg dz Dm^ fp dDv +fg y dz Dv f a dDs ^fg T dz Ds,
\
(62
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
any of the various surfaces of discontinuity by the temperature and potentials at the If the variations of t and J/,, il/g, etc. are to be point considered. neglected, the variations of p and a will be determined solely by the change in position of the point considered. Therefore, by (612) and
o'
at
any point
in
(614),
dp=.
gy
dz.,
da = g Fdz
and
J.
W. Gibbs
453
dE= ^fp cWv /dp Dv\f(3 dDs +fda Ds =  dfp I)v + d/G Ds.
If
(622)
we now
f/,
commencing
at the
given
we
obtain
AE=
where
(623)
tem diminished by
variations,
and
is
without
The condition of
(6 24)
fpDv^j'ffDs
has a
(625)
o',
maximum
0"
p and
mass
(In ordin
ary cases
tinuity,
may
and jt? as a linear function of z in each different mass.) It may easily be shown (compare page 416) that this condition is always sufficient for stability with reference to motion of surfiices of discontinuity, even
when
the variations of
t,
M^, M2,
etc.
cannot be neg
0)1
the Possibility
of
the Forination
When more
may
conceive of a
new
surface
in a
being formed between any two of the masses which do not meet
sui'face in the original state of the
system.
The condition of
stability
by
exemplified
by a system which
is
is in
equilibrium when
a very small
formed.
us suppose that there are four
To
fix
our ideas,
let
homogeneous
surfaces,
all
in four
which we
along a
may
call
meeting
line L.
This
indicated in figure 11
by
454
J.
ISubstances.
In an
infini
we may conceive of a
(to
and C
be called AC),
by the same
Fig.
U.
Fig. 12.
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 O' and O" where they We may therefore form a quadriare cut by the plane of section. lateral of which the sides af5, f:iy, yd, 6(x are equal in numerical
value to the tensions of the several surfaces AB, BC, CD, DA, and are parallel to the normals to these surfaces at the point O
in
we can
surfaces of discontinuity meeting at O' and O". But the directions of the normals to the surfaces AB and BC at O' and to CD and DA at O" in the varied state of the system diifer infinitely little from the directions of the corresponding norrelations to the
mals at
as
We
may
meeting at
O',
two
at O".
Therefore,
we
direction of the normal to the surface AC, and the value of its tenIf the tension of a surface between such masses as A and C had sion.
it is
would have
been stable with respect to the possible formation of any such surIf the tension had been less, the state of the system would face.
have been
unstable
ill
at least
practically unstable.
To determine whether
it is
it is
prop
J.
W. Gihbs
455
refined
analysis than
The
result
generalized as follows.
than three surfaces of discontinuity in a fluid system meet in equilibrium along a line, with respect to the surfaces and masses
When more
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 the sides to these surfaces, each side being perpendicular to the corresponding
surface,
and equal
to its tension.
With
new
less,
is stable, if every diagonal of the polygon is and practically unstable, if any diagonal is greater, than the tension which woidd belong to the surface of discontinuity between
when
the diagonal
tem 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.
all
But when,
in
is
structed for
*
We may here
in the
stability
lines in
which surfaces
manner
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
sum
tension of the line L, this line will be in strictness stable (although practically unstable)
and
C,
when
little less
The
paper need
system
is
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
relating to surfaces of
same order of magnitude as the quantities discontinuity which were neglected. But where surfaces of
is
III.
58
March,
1878.
456
J.
W. Gibhs
a certain diagonal
in
For
method described on
page 413
is
evidently applicable.
A
rium,
similar proposition
may be
enunciated in
many
is
If these
the lines in which these edges meet, the edges being perpendicular
to the corresponding surfaces, and equal to their tensions, and the
sides being perpendicular to the corresponding lines.
solid angles in the physical
Now
if
the
may
be subtended by
the sides and bases of a triangular prism enclosing the vertical point,
or can be derived from such
by deformation,
the tensions will have the form of two triangular pyramids on opposite sides of the
ally unstable
same base, and the system will be stable or practicwith respect to the formation of a surface between the
in a point,
is
in
which
The Conditions of Stability for Fluids relating to the Formation of a New Phase at a Litie in which Tliree Surfaces of
Discontinuity meet.
With regard
to the formation of
new phases
We may
which
be
there are three such surfaces, this being the only one of frequent occurrence,
in a straight line.
It
will
which such a
by a filament of a
difterent phase.
fluid masses,
A, B, and C,
by
meet in a straight
being
less
each of the surfacetensions Cab? ^bcj <^ca Let us suppose that the
J.
W. Gibhs
457
system
is
which
is
cylindrical surfaces
straiglit lines.
which the full lines represent a section perpendicular to all the The system thus modified is to be in equilibrium, as well as the original system, the position of the surfaces AB, BC, CA being unchanged. That the last condition is consistent with equili14, in
surfaces.
brium
will
considerations.
Fig. 14.
Fig. 15.
Fig. 16.
Let Vd denote the volume of the mass D per unit of length or the area ab c. Equilibrium is evidently possible for
any values of the surfacetensions (if only Cab, o'bc? ^ca satisfy the conmentioned above, and the tensions of the three surfaces meeting at each of the edges of D satisfy a similar condition) with any
dition
if the edges of D are constrained to remain AB, BC, and CA, or these surfaces extended,
will
be bounded
by only two
of
cylindrical surfaces.)
in
We
by
may
system as maintained
equilibrium
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 immaterial when it is rigid, and no forces external to the system Avould be required to keep a corresponding part of the original system in But it is evident from the points of application and equilibrium. directions of these forces that they cannot have a zero iesultant unless each force is zero. We may therefore introduce a fourth mass D without disturbing the parts which remain of the surfaces AB, BC,
and acting
at right angles to
CD.
It will
be observed that
[See (615).]
all
the angles at ,
b, c,
and d
in figure 14
O'dc
by the six surfacetensions Cak, Cbc, o'ca, (5'da, The angles may be derived from the tensions
458
J.
W. Gibhs
by the following construction, which will also indicate sorae important properties. If we form a triangle a ft y (figure 15 or 16) having sides
equal to
(Tab, o^bc?
be supplements
we may suppose the sides of the triangle to be perpendicular to the surfaces at d. Upon p y we may then construct (as in figure 16) a triangle ft y 6' having sides equal to Cbc, ^dc? ^db, upon y a triangle ;/ a 6" having sides equal to
of the angles at
d.
To
fix
our ideas,
2i
^CA,
<5'ab,
oTda,
<3'db5
Cdc,
cTda.
antl iipon
<!'
/i
ft
y,
a,
ft,
ft
y.
The angles
of
discontinuity at a,
b,
and
in
c.
Thus
ft
y d'=.da
b,
and a y S"=zdb
a.
Now
a
ft
if S'
and d"
will
fall
together
in a single
y,
6'"
fall
ft
In this
case
we
shall
have
curvilinear triangle
y 6 \a y 6=.a y ft, and the three a db will be together equal to two
angles of the
right angles.
of the three angles of each of the triangles of the three angles of the triangle abc.
But
6", 6'"
it is
do not
fall
ft
y,
<5'dcj
by diminishing some or all of these tensions. (This will easily appear when one of the points S', 6", 6'" 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
6',
greatest of the tensions Cd^, Cdb, ^dc the two greatest, when these are equal, and all three when they all are equal to diminish until
a ft
y,
we may suppose
the
6',
S", 6'"
is
ft
y.)
case
we may
new
surfaces are
by the distances of an
in
a ft 6'",
ft
yd", y a 6"
when
the ten
(Tda, Cdb,
1
little
6,
bdc,
cda
and the sum of the angles of each of the triangles adb, will be greater than two right angles.
J.
W. Gihhs
459
Let us denote by
the
and
ahd', and
ah, c
d,
ad,b d.
<5da ^DA "T
Also
let
"'^S ^^^
^DB ^DB
TFv
"T" '^'dC
*DC
^AB ^AB
<5'bc
S^q
Oqa
^Ca?
(626) (627)
and
=^^d ^d
The general
of
fixed,
may
tliis
be written
2{(}6s):S{pdv)
[See (606).]
If
Q.
(628)
we apply
by the
intro
duction of the mass D, and take the difference of the results, suppos
we
have
(^da
<^Sab ~ O'bc ^Hc + Odb (^Sdb + Cdc <^dc (TcA ^ScK  Pt> ^Vj) + Pj, Svj, f ps <Svb + Pc ^Vc =
(5'ab
^da
0.
(629)
if
we
differentiate (626)
we
dWs dWv = SdA ^^Oda + Sdb f^ODB + DC ^ffj^c  AB C^O'aB **BC t?0'BC CA f^^cALet us
(630)
now suppose
size,
remaining always
the quantities
tc.
ratio,
SDA<?<?'DA=if^(^DA*'DA),
S^B (^^mi
=^
d{(^I,B Sdb),
CtC.
(631)
We
TFs
TTv
O'bcSbc
 C^ca^ca),
(632)
whence, by (626),
= 2 Wy,
when
(633)
The
460
J.
W. Gibbs
pj^^ jOg,
he a minimum under any constant values of we may make Wp so small that when it
shall
W^ Now
for
system remaining
in
we may
d a, d b, d c, and regard
itself.
the figure
abed
be, c
as remaining similar to
For the
total curvature
(^. e.,
b,
may
be regarded as con
adb,bdc,cda
if j^d
Therefore,
when
Vi,
is
so
and
the tensions
ab c d, and
Wy
This shows that the system cannot be stable for constant pressures
and tensions when v^ is small and TFy is positive, since Ws Wy It also shows that the system is stable will not be a minimum. when Wy is negative. For, to determine whether TP^ Wy is a minimum for constant values of the pressures and tensions, it will evidently be sufiicient to consider such varied forms of the system as give the least value to W^ IVy for any value ot vd 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 j^d 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,
fluid
in
D.
The components
tliat
D must of course be such as are found We shall regard p^ and o'da, Cdb, o'oq as
D
which
satisfies
determined by
potentials.
phase of
to
temperature and
the
DB, DC, from the temperature and potentials of the given system. Let us first consider the case in which the tensions, thus determined, can be represented as in figure 15, and
sistent with the equilibrium of a small
pj)
considering.
It
J.
W. Gibbs
461
that
its
alone,
and
we may suppose
jOa? i>B5
figure
abed
make
jOp
pressures, since
supposed that
this quantity
We
may
of
y^,
manner.
We
^d in terms of the tensions in the following shall write [D B C], [D C A], etc., to denote the areas
^b,
^c,
?'b
triangle
bdc.
:
triangle
udc
be sin bed
sin
ac sin acd
:
da/J sin
:
:
sin
ySp
Sfi
sin
:
yda 6a
triangle
y 6 fi
:
triangle
[D
B C] [D C A].
(634)
Hence,
yA:yB:^^c:^D::[DBC]:[DCA]:[DAB]:[ABC],
where
4V[(0'ab+<5'bc+0'ca)(0'ab+0'bc 0'ca)(0'bc+0ca~0ab) (o'ca+O'ab
O'ec)]
may be
written for [A
symbols, the sign \/ denoting the positive root of the necessarily positive expression
which
follows.
case of equilibrium,
when the
and vD is sufficiently small. Now if pA=i*B =/>c5 I^d will have the same value, and we shall have by (627) Wy := 0, and by (633) Ws 0. But when Vq is very small, the value of TFg is entirely determined by the tensions and Vo. Therefore, whenever the tensions satisfy the condition supposed, and ?Jd is very small (whether pj^, p^, p^ are
equal or unequal,)
=: TFs
i?A ?^a
 IH Vb  Pc Vc,
(635)
^^ ""
Since this
is
[D B C]
[D C A]
[D
A B]
'
is
possible
when
462
J^.
W. Gihhs
small,
it
follows
when
jy^
C meet
has
at least
fluid
When p^
a greater value,
practically unstable,
e.,
if
D
If
should be formed
it
would tend to
increase.
in
Let
us
next
new
the pressures and tensions are consistent with equilibrium for any
vq,
tri
be together
less
and the
a b,b
c,
c , will
For
given values of the pressures and tensions, it will be easy to deterFor the tensions will give the total mine the magnitude of v^.
curvatures (in degrees) of the lines ab, be, ca; and the pressures
will give the radii of curvature.
These
lines
determined.
In order that
po shall
vd
shall
be very small
is
evidently
necessary that
be
less
Yet
if
the
tensions of the
new
represented as in figure
of
pr,
Vp
may be
new
quite small
when
the value
is
only a
little less
In any
case
when the
tensions of the
sented as in figure 15, and v^ is small, W^ is negative, and the equiMoreover, TFg is stable. W^, which reprelibrium of the mass sents the work necessary to form the mass D with its surfaces in
place of the other masses and siu'faces, is negative. With respect to the stability of a line in which the surfaces AB,
tensions of the
new surfaces are too small to we first observe that when the pressures to make Wp moderately small but not so [this will be when po is somewhat smaller
member
of (636),
more or
less smaller
according as
differ
more
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
tensions)
p^ (with the same values of the other pressures and the the same will be true. For somewhat smaller values of pn,
which
will
we may
meeting
/)o,
CA
as
For
still
smaller values of
we may
CA
as capable
J.
W. Gibbs
463
may
as
determined
the conception of a
by our equations, becomes quite insensible, small mass D having the properties deducible
in
the
be
in
But
The
new
Let us sup
much
When
make
to
which
it
relates
less
when somewhat greater than the second member of (636), more or greater according as the tensions differ more or less from such as
CA meet
tive.
will
of such a mass as
we have
considered, since
W^ Wy
jOr,.
will be posi
The same
of jOp, the value of TFg  TFy, which measures the stability with respect
to the kind of change considered, diminishes.
finite
values of
p^.
as
we now
suppose,
we must
also
which the surfaces DA, DB, DC meet together (with the surfaces in two opposite points. If such a figure is to be in equilibrium, the six tensions must be such as can be represented by
* See note on page 455.
We may here
may have
a negative value.
three surfaces of discontinuity are regarded as meeting, but where nevertheless there
reaUy exists in stable equilibrium a filament of different phase from the three surrounding masses.
The value
would be
(For the
linear
W^
it
would be necessary
We may
The reader
we must
recog
nize a certain negative tension in the line of intersection of the three surfaces of
discontinuity.
III.
59
March,
1878.
464
'L
ISubstances.
condition
If
size
we denote by mv
and form
?0s
it
D (of such
and by
new
may
easily
that wJs=f^vpositive
be shown by a method similar to that used on page 459 From this we obtain ^s~^v=i^'v This is evidently
greater than the other pressures.
when p^ is
But
it
diminishes
with increase of
jf^,
values of
will
px))
so long as our
as accurate,
which
be so long as
size.
has a sensible
new
surfaces are
much
which
in
by
would take
if
it
should be
formed, since
it
is
we have
pair the stability of the line considered, as deditced from our equations.
Nor
demonstrated
may
fail
to be realized
when
is
(See
page
The Condition of Stability for Fluids relating to the Formation of a New Phase at a Point lohere the Vertices of Four Different Masses meet.
Let four different
DC, which meet
lines fluid
masses A, B, C,
meeting
in other respects,
tical point
Let us suppose the system stable and consider the conditions of stability for the ver
mass E.
J.
W. Gibbs
465
If the
system can be
equilibrium
when the
is
evident that
will
have
will
and
E.)
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
meet,
would distribute itself along some of the lines or surfaces which meet at the vertical point, and it is therefore sufficient to consider the stability of these lines and surWe shall suppose that the relations mentioned are satisfied. faces. If we denote by TP^^ the work gained in forming the mass E (of
a mass
should be formed,
it
l)e in
by W^ the work
ex
pended
in
may
easily
whence
also, that
W^, Wy=^W.,;
when
the
volume
is
will
be
W^ and W^
when
all
tensions
may
then be represented in
by the
AB and the direction of its normal The point f will lie within the tetrahedron formed by the other points. If we write i'e for the volume of E, and
y,
6, , viz.,
the tension of
line
a /5,
etc.
are suppressed to
make room
for E,
we have evidently
(639)
0.
all
Wg,=
Now
always possible for a given small value of v^ with any given values of the tensions and oi' p^, j^^, 2^c, Pt> When the tensions
satisfy the critical relation,
W^ =
0, if
p^
But when
jo^,
v^
Pb,
is
Pc
by the
may be
neglected.
466
J.
W. Gibbs
relation
is
satisfied
and
v^.
small.
This
?.>a,
(640)
all
we may suppose
the
Then
E
is
will
may
be called
named
after the
mass which
of
^c?
be the volumes
may be
^d will divided
e.
The
a fd y S e, common to the
yS
^,
we
recollect
common
to the lines
y6.,6s,ey,
and so in other cases, (it will be observed that y, 6, and are the letters which do not correspond to a or b) also that the surface abc is the surface DE and therefore perpendicto the surface
ular to 6
f, etc.
etc.
the tetrahedron or the area of the triangle specified, sin (ab, be),
ein (abc, dbc), sin (abc, ad), etc. the sines of the angles
made by
etc.,
the
lines
and surfaces
specified,
and [B
CD E],
[C
D E A],
the vol
umes of tetrahedra having edges equal to the tensions of the surfaces Then, since we may express the between the masses specified. 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 w^hich 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,
v^
:
t'B
tetr
bcde
tetr
acde
:
be
sin {ySs,
aSs)
sin (/i^^f,
(i^f:i)
pade
aSe
'
tetr
trian
tetr yfide
:
tetr
:
yade
[B
C D E]
[C
D E A].
Hence,
^'a:Wb:^>c:''d::[BCDE]:[CDEA]:[DEAB]:EABC],(641)
and (640)
^'^
may be
written
,^^^.
J.
Wi Gihhs
467
is less
when the
D meet is any mass of the nature of E. But if the value of p^, is greater, either the masses A, B, C, I) cannot meet at a point in equilibrium, or the equilibrium will be at least
point where vertices of the masses A, B, C,
stable with respect to the formation of
practically unstable.
When
new
critical relation
vex toward
when
In the
first
case,
71 y
is
meeting
is
at a point
This
sub
when
/>e is
it
mass
which
will
form
Avill
be so small that
is
may
be neglected.
This will
when p^
smaller
in
than the second number of (642). In the second case, the equilibrium of tlie five masses A, B, C, D, E will be unstable, but the equilibrium
of the four masses A, B, C,
will
is
of insensible magnitude.
jt>E is
greater
considerably greater
member
of (642).
JAquid Films.
When
between other
thickness
fluids,
Avill
give
even when
its
is sufficient
The
fix
fre
films,
To
our
we
are
shall
is
gaseous.
The reader
will
its
Let us imagine the film to be divided by surfaces perpendicular to sides into small portions of which all the dimensions are of the
as the thickness of the film,
is
such portions
of
the film.., \t
approximate equilibrium between the difierent parts of any such element and the other fluids which are immediately contiguous, than for the attainment of equi
468
J.
W. Gihbs
librium between
all
There
will
elements
may be regarded
all
as satisfying the
conditions of internal equilibrium, and of equilibrium with the contigiaous gases, while they
may
not satisfy
It is M^ien the
changes due to
itself to
want
oi
except so far as
it
accommodates
it
any change
in the
is
properties of the film are most striking and most sharply defined.
Let us tlierefore consider the properties which will belong to a film have the properties of matter in
all
its
elements
is
each element
regarded as invariable, with the exception of certain substances which are components of the contiguous gasmasses and have their
potentials thereby determined.
cisely satisfies these conditions
The occurrence
may
sion of this
somewhat
principal
general.
Let us
first
ele
under the conditions mentioned. Let us suppose ment while the temperature and the potentials extended, the element which are determined by the contiguous gasmasses 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
of the film
surfaces.
The same
is
will
one com
we regard
by
dividing surfaces which make the surfacedensity of this component vanish, the thickness will vary inversely as the area of the ele
ment of the
film,
in the
nature or
the tension 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.
in those cases in
itself
J.
W. Gibhs
469
When
on
its suifaces,
be found
in greater proi>ortion
on the surfaces.
When
the film
is
ex
The value
of the elasticity
of
its
the film.,
{i.
e.,
surfaces divided
face),
by the
be calculated from the quantities which specify the nature of the film, when the fundamental equations of the interior mass, of
are
may
known.
We may
illustrate this
by
a simple example.
Let us suppose that the two surfaces of a plane film are entirely
alike, that
Let us
call these
Let us denote by y
surfaces
and
j/g ^^he
densities
by such dividing
of the film
tities
and So in the part of the film extended are invariable, as temperature and the potentials of the other components. also the
of
/Nj
From
the definition of JS
we have
2dff
= B,
s
(643)
film
d{X
)/j)
d{X y^
2 ^2(1))
(644)
^ri
Hence we obtain
\ y^
^X3+2/'2(i)
=. y
ds
d\
A dy^.,
(^
r2
+ 2 ^2( 1)) =
72
<^^
'^
(h'2
2 f?^2(i)
470
J.
W.
(xibbs
^Vi'^^^^d^rJ^2^v=^ri(b'2\^ri^b'i s
If
we
set
= ll,
y.'
'
(646)
we have
and
2 I\^^^
.j,
^ y^dy^nXldy,
(647)
ds
= \ y^dr 2d^2^^,.
eliminate ds from (643).
relation [see (514)]
(648)
With
tliis
equation
we may
We may
also
eliminate dcf
by the necessary
dff =^
^2(1)^^2
This
Avill
give
4 / 2^2 ^^,^
^ (A ^^ dr^2 dP^,,,),
(649)
or
^^4^= A y,
where the
tions that the temperature
~+
all
%^\
/u^
(650)
and
and
//g
are constant,
The
latter con
may he
ir iVi') '^Mi
in
f
=
in
o,
(65i)
in
densities of
and S^
the con
tiguous gasmasses.
[See (98).]
When
its interior
and
masses are known in terms of the temperature and potentials, equation (650) will give the value of
E in
together with
If
A.
we write G^ and G^
and
S.^
per
we have
G,=:ly
G,=Ay,\2r,,,,^,
Therefore,
(652) (653)
G^=G,r+2l\^,
(p)
=A;.,i^+2^i^lll,
(654)
where the difierential coefficients in the second member are to be determined as in (650), and that in the first member with the additional condition that
is
constant.
Therefore,
J.
W. Gibbs
471
\ dfi^
k
the last differential coefficient being determined by the same condiIt will be observed that the
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 gasmasses are regarded as constant, and the poten
value of
other components,
yu,
and
ju.^,
considered.
The
increase
of
The
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
same
is
film
be altered,
if
rior drains
away
may
reduced by evaporation, the tension be either increased or diminished. (The evaporation of the sub/S'j,
stance
in
the case
it
we have
easily be
just considered,
tension.)
Yet
may
When
a plane film
equality
original position
It
is
we may
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 an other, the lighter portions of the film will dart from one side to the
other, so as to
show
The
March,
differ
movements
60
472
J.
W. Gihhs
we account
for the
increase of tension
viscosity,
will
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 con
its
This
is
phenomena
is
of the
is
phenomena
the immediate
an increase of
its
tension,
by which
it is
The phenomena
is
to
which we have referred are such as are apparent In the following experiment, which
increased tension
is
described
by M. Plateau,* an
manifested in a
of a
The warmth
which
thin enough to
show
appear indicating
a diminution of thickness.
When
the finger
is
returns to
its
original color.
would be
resisted
by any
rior to
so far supposed that the film is thick enough for its intehave the properties of matter in mass. Its properties are then entirely determined by those of the three phases and the two surfaces
We have
of discontinuity.
From
these
we can
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
limit.
Yet a
which we
may
* " Statique experimentale et theorique des liquides soumis aux seules forces moleculaires," vol.
i,
p.
294.
J.
W. Gihhs
473
relates to
not
satisfied.
With
bution of
its
components, a film
general be stable,
when
its
interior has the properties of matter in mass, with the single exception
of variations afiecting
its
With
neutral.
is
become unstable
in this respect.
For
it is
when
it
sufficiently
first effect
reduced
in tliickness,
it is
most natural
to
suppose that
the
(We
liquid films
In certain other cases, the between gaseous masses. opposite supposition might be more natural, as in respect to a film of
air,
when
sufficiently
reduced
in thickness.)
Let us
now
is
thick
enough
mass, and
tiguous gasmasses
and
several elements,
such a film
may
between the contiguous gasmasses (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
That
is,
the
when by a we understand
sum of the tensions of the two surfaces of 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
(this is
equivalent to the
by
/" its
474
J.
W. Gihbs
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 Fin (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 homogeneous mass in the form of a thin sheet bounded 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
as an approximately
in
(612),
which requires
it
z,
and condiit
which makes
a certain
Nor can
free
to
move independently
of the surfaces,
which
is
contrary to what
we have supposed.
is
horizontal.
For
if
these condi
were
we
form any exception to the principle indicated on page 450, that when a surface of discontinuity which satisfies the conditions of
mechanical equilibrium has only one component which is not found in the contiguous masses, and these masses satisfy all the conditions
of equilibrium, the j^otential for the component mentioned must satisfy the law expressed in (617), as a consequence of the condition of mechanical equilibrium (614). Therefore, as we have just seen that
it is
impossible that
all
is
not horiit
when
the temperature
is
uniform,
is
not due
must have
nioie
(617).
J.
W. Gihbs
475
The
difficulties of
entirely ful
effect
made
for such
most symmetrically The rises to the top of a mass of the liquid. motion of the liquid, as it is displaced by the bubble, is evidently such as to stretch the two surfaces in which the liquid meets the air, This will cause an where these surfaces approach one another. increase of tension, which will tend to restrain the extension of the The extent to which this effect is produced will vary with surfaces.
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
But
this
running out of
it is
by
its
viscosity as soon as
film,
and the
increasing
their
tension will
more permanent
faces.
able for supplying the substances which go to form the increased sur
We
may form
is
by
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
V= 581 Z)3,
where
(656)
[i. e.,
V denotes
the
mean
that velocity
xl, S.
The
calculation of formula (656) and that of the factor (5) applied to the formula
of Poiseuille,
to adapt it to a current between plane surfaces, have been made by means of the general equations of the motion of a viscous liquid as given in the memoir referred to.
476
which,
J.
W. Gihbs
if it
fixed planes,
whole space between the would give the same discharge of water as the actual
sup
in
This
337 Z>3
is
water
in
equivalent to
(657)
F=r
for descent
899 Z>2
between
parallel planes.
The numerical
coeflicient in this
is
equation
difi^ers
derived from
at least con
we may
mentioned the mean velocity of the interior relatively to the surfaces This is a velocity of .1""" per will not probably exceed 1000 D^. ,06"' .01""", per minute for a thickness of second for a thickness of
.001
fifth
order in a film of
water), and .036'" per Jiour for a thickness of .0001"' (which corre
sponds to the white of the first order). Such an internal current evidently consistent with great persistence of the film, especially
those cases in which
tenuity.
tlie
is
in
On
be formed without carrying up any great weight of liquid, and any such thicknesses as these can have only a momentary existence.
consideration will show that the phenomenon is essentially 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
of the
A little
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 gre'atest to the least thickness of the film. During this extension, as well as at other times, the increased elas
due to imperfect communication of heat, etc., will serve to protect the bubble from fracture by shocks received from the air or the
ticity
* Ibid., p. 653
;
ix, p. 5.32.
J.
W. Gibbs
477
pipe.
If the
bubble
tion
(613) will
The bubble
will then
ing to the top, more or less slowly, according to the viscosity of the
film.
The
and
due partly to the greater tension to which the upper parts are subject, and partly to a diflerence in the matter of which they are composed. When the film has only two components of which the potentials are not determined by the con
may
components S^ and S.^, the latter denoting (as on page 469) 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,
quantity of
less ratio.
in the first
element as
When
and
have the
be subject to the
viscosity
we have already described, if it is truly fluid, howmay be. It seems probable, however, that
in virtue of
process
may have
those which are caused by gravity in the interior of a vejy thin film
which
potent
satisfies
However
in
this
may
be, there
in
is
is
often
more
its
producing changes
This will be seen
film is terminated.
a film,
when the
where the
is
bounded by concave
surfaces,
less
film.
thickness
is
This
efiect
best seen
when
a film
Unless diminished thickness near the edge causes a rapid upwai'd current on each side, Avhile the central portion slowly
very viscous,
its
478
J.
W. Gibbs
film, where the edge is nearlywhich have become thinned escape from their position of unstable equilibrimn 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.
descends.
horizontal, portions
suction which
produces these
effects
may be
in
following considerations.
The pressure
is
the
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 centimetre in height. (It
is
probable that
much
At
point near
by
Now if the difference of pressure of these two points were distributed uniformly through the space of one centimetre, 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
atmosphere.
a small fraction of a millimetre),
its effect in
producing a current
in a
limited
gravity.
space must be
that of
the
There
the
is
a third
film, we may regard it as downward tendency of the interior of the way in which this descent may take place,
when
principal
air.
component of the
interior
is
volatile,
viz.,
if
through the
we
be 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 practhe same value in the atmosphere as in the film,
it
may
easily
tical
importance.
potential for water in the atmosphere differs con
dry atmosphere, or a
J.
W. Gihhs
tlie
479
atmospliere,
neglected.
film will
cftfct of
tirst
not to be
In the
be accelerated, in the second, retarded. In the case of the film containing glycerine, it should be observed that the water condensed cannot
in
all
down by
the
,
internal current but that the two processes together will tend to
wash oiit But when a com])onent which greatly diminishes the tension of the
film,
its
mass, (therefore
evaporation
of and condensation may the suithe film as in the potential for that component is the same in rounding atmosphere. To illustrate this, let us take the simple case of two components /S'j and xS'^, as before. (See page 469.) It appears from equation (508) that the potentials must vary in the film with the height 3, since the tension does, and from (98) that these varia
be considerable, even
tions
;/j
densities of S^
and
S.^
film.
The
level
to another
therefore as
much more
is
as its
and condensation of the two substances are the same, these processes It will be will go on much more rapidly with respect to S^.
observed that the values of
^
dz
and
^
dz
it
will
have opposite
sigiis,
down through
Moreover,
So,
may
easily be
evaporation or condensation of
effect
will
S^.
These
efi'ects
same kind.
it
For
if
condensation
will cause a
diminution of
which
/Sj.
its
and thus occasion an extension of this part of the film, by thickness will be reduced, as it would be by evaporation of
infer that
it is
We may
But apart
we have
seen that a
April, 1878.
48C
filiii
J.
W. Gibbs
is
which
by the
and the suction at its edge. Sooner or, later, the interior wall somewhere cease to have the properties of matter in mass. The film will
then probably become unstable with respect to a flux of the interior
page 473), the thinnest parts tending to become still more thin any external cause) very much as if there were an attraction between the surfaces of the film, insensible at greater dis(see
(apart from
tances, but
film is
suffi
ciently reduced.
We
is
of soapwater, however, the rupture does not take place, and the
processes which go on can be watched.
superficial observation that a film of
It is
which the
approaching
interrupted
by
black spots.
That
in
is
shown by the
made
single
This
is
film,
when a
black spot breaks out and spreads rapidly over a considerable area
Avhich was before of a nearly uniform tint approaching the black. The edge of the black spot as it sj^reads is marked as it were by a
which unite together on touching, and thrus Under across the bands of color below. favorable circumstances, there is often quite a shower of these bright
string of bright beads,
larger, glide
becoming
spots.
down
They
much
thicker
appar
ently
many
times thicker
than
Now
if
The thickening of the edge of the film ance would For an extension of the for by contraction. cannot be accounted film and contraction of the lower and thicker upper portion of the 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 But the rapid formation of a thin spot by an internal described.
be presented.
current would cause an accumidation 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.
J.
W. Gibbs
is
481
That which
black spots
ner.
It
most
account for
iu the
fonuatiou of the
is tlie
by
grows
thin
if possible.,
by passive
the film.
it
flux of
matter from
its interioi,
same process. On the other hand, gelatinous properties are very marked in soapwater 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 (wdiere we know that the soap or some of its conii)onents exists in excess), or throughout a film which is so thin that the interior has ceased to have the })roperties of matter 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 with respect to extension,
soap (or of some of
the interior of the
its
film.
necessary for
its
stability
connected with
an
excess
of
the
film.
With
the interior has ceased to have the properties of matter in mass, and
not be applicable,
extension
it
is
reference to
still exists.
we account
density
of
arrest
of
internal
currents
by
the increasing
soap or some of
still
its
components
in the interior of
the film,
we must
in the
difteience of
composition
interior
been obliterated.
The preceding
gas.
liquids or
to films of gas
between
* 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 soapwater,
anj^ greater
superficial
we
are considering,
is
But the resistance to an internal current, such as not necessarily measured by the resistance to such motions
to.
482
J.
W. Gibbs
liquid.
masses of
liquid.
may
the surface of a
mass
of the
same or a
is
different
This
may
be done
is
formed by a bubble of
(If
air ris
volume
drop.)
have precisely the same form, as bound the l)ubl)le and the
momentum
air,
of the
drop
carry
it falls, it
appears
which
is
the counterSince,
howin
component of
tlie
side of the air film, the necessary differences of the potential of this
persistence
compared with
In this
greatly reduced.
Compare page
479.
and
Fluids.
We
by
far the
any rigorous treatment, since the masses are necessarily isotropic both in nature and in their state of strain. In
for
On
is
any tendency of the surfaces of discontinuity to variation in area or form may be neglected in comparison with the forces which are pi"oduced in the interior of the solids by any sensible strains, so that it
is
They
are distinguish
able from ordinary airbubbles by their general behavior and by their appearance.
one appearcourse an
Tliis is of
tlie li(j\iid.
J. TF.
Gihhs
Equillbriinti of
fluids
IIeteroge)ieoiis Stihstances.
483
between
solids
and
and a
line structure,
compatible with a
shall not exclude
We
we
is
it
{i.
e.^
of the nonhoiiio
and the quantities of the foreign substances which may be ])resent. The notions of the divkUng 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
separates,
(see
pages 380 and 386), will evidently ^pply without modification to We shall use the suffix with reference to the
,
The
suj)erficial
and of the
may
page 397),
^S(l)5
VhDI
^ 2(1)J
^ 3(1)5
6tc.
ff
^=^S(i)^Vs(i,/^2 ^2U)/^3^^3(l)etC.,
in
which
yUg? /^s?
^^c.
the potentials
As
0'
in the case of
as expressing the
of discontinuity
specify
but
two fluid masses, (see page 421,) we may regard work spent in forming a unit of the surfiice under certain conditions, which we need not here
latter quantity
it
of the surface.
The
G depends upon
the
work
spent
m forming
the surface.
With
these processes are not distinguishable, unless the surface of discontinuity has com2:)onents which are not found in the contiguous masses,
and even
must be supposed
to be
formed
out of matter supplied at the same potentials which belong to the matter in the surface,) the
work
484
nially
J.
Substances.
by stretching
masses
is
and
its states
there
surface
With
we now
when
at
it
meets a
fluid,
It will
be necessary
for us to
is
it
may be
by the
state of strain
minima.f
line
may
discussion.
we
Let us consider
may
and
let
By applying
we
can
make
all stress
vanish in
forces,
its interior.
The
tensions of the
two
may
evidently have different values in different directions, and are entirely different
from the quantity which we denote by a, 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.
it
not greatly
This
is
numerous
as solids,
its
fluid,
solid state
has been by
insensible gradations,
ficial
we may
as they
may be
differently affected
stresses applied to
was decidedly solid, and that they will only differ so far by subsequent variations of temperature and of tlie Moreover, when an amorphous solid is in a state of the solid.
it
may have no
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 a will coincide with the superficial
The
J.
W.
Gihhi<
485
its effect
on
quite otherwise
solids are
fluid in
which
can dissolve
is
bounded
in
For
may
be deduced
as follows.
we suppose
is
is dissolved at the surface where it meets the and that the fluid is considerable in quantity and remains homogeneous, the increment of energy in the vicinity of the siirface
infinitesimal portion
fluid,
will
where
is
Ds
its
])Osition
dissolved),
and
Cg
its
principal
curvatures
solid),
(positive
when
%!, the surfacedensity of energy, e^' and y" the volumedensities of energy in the solid and fluid respectively, and the sign of integration relates to the elements Ds. In like manner, the inciements of entropy and of the quantities of the several components in the vicinity of the surface
their centers
will
be
.fVh'Vv"
(<''l4''3) '/SU)]
S^^J^S,
etc.
The entropy and the matter of different kinds represented by these 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
is
the
wdiole
space
occupied
by the
solid.
fluid
except
that
which
regarded as constant, the increment of energy in this space obtained [according to equation (12)] by multiplying the above
expression relating to entropy
may be may be
to
by t, and those
relating
the
components by
* The potential
is
,
yw^",
"
^2^ tc.,*
If to this
//
is
and to distinguish
fi
486
J.
W. Gibbs
we add
Now
By
by
(93)
we have
r=
//'
f,"
t ,1,"
+ ///' ;//' +
//^
y/ +
etc.
this equation in
energy
and (659), our expression for the total increment of the system may be reduced to the form
/[fv'
(660)
is
necessary
tion of equilibrium
^,,^eVtv.J+if + i^e,+e.^a^
y
This equation
containing
(7,
\
(061)
is
plane.*
sti'esses
when
(<^'i
tlie solid
has no
except an
by
ff is
c^) ^
^^'^^^
member
represent [see equation (93)] the A'alue of the potential in the solid
for the substance of
which
it
consists.
equation reduces to
that
is, it
the same
fluid.
all solids is
+ (c^ +^2) ^
with
the actual temperature will have sensibly the same values as Hence, the second lated for the true pressure of the solid.
relatina; to tlie solid
if calcu
member
we
mass (when
shall see,
may
The other
potentials
fi^, 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.)
relates to substances
The expressions
value zero.
have the
is
denoted by
T,
which
is
therefore
7/
in (661).
J.
W. Gibbs
E<piilibrhiiii
when the
of Il'eterogeneovs
Stibstauces.
487
of eciuatioii (661),
tropic,
is
\ {ci {
may be
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 difterence of the
two
aud
v'
second
member
of the ecpiation
may be
if
c^)
ff
represented the true pressure in the solid in the direction of the nor
Therefore,
we had taken
for
fluid, as it
does
when both
which
is
would
not have led us into any })ractical error in determining the value of
the potential
/<,"
On
the other
hand,
if
differs
in (661) will
make the second member of the equation equal to when the stresses are isotropic, but this will not
/./
," in
\
c^
0.
the stresses in the solid are not isotropic, equation (661) be regarded as exi)ressing the condition of equilibrium with respect to the dissolving of the solid, and is to be distinguished from
When
may
of isotropic stress.
crystalline bodies,
jj^"
matter
a little less than that necessary for equilibrium with respect In regard to the actual behavior of
all
by the equation for the solid with its distorting stresses, and that new matter will not be formed if the value of /<i" is less than the same equation would give for the case of
tial yu/' is
It
new
solid matter
here
left
out of account.
134137, but without reference to the state of strain of the solid or the influence of
the curvature of the surface of discontinuity.
III.
62
488
if
tT.
W. Gibhs
fluid,
solid,
and then,
if
isotropic stress
is
would be
commence and go on
The
but
it
equilibrium for any single point at which the fluid meets the solid,
will cause the values oi
by
p" and yu/' in (661) to vary according If we suppose that the (612) and (6] 7). in a state of isotropic stress, which is the
it is
most important
is in
case, since
at
least
that
stance of the solid which would belong to the solid mass at the
temperature
Or,
if
{Ci^c.^)
G must be equal
the condition
to ///'.
we denote by
t
temperature
may be
(662)
(y)z=y'+(c,+
C2)(7.
Now
By
if Ave
write
;/"
we have by
(612)
dp)"=gy"dz.
(98)
d{p')^y^di.i^\
d^i^' =z
and by (617)
</
</
dz
1
'
whence
Accordingly we have
d {p')
=1
^^^
d{p')^dp"
and
z being
= g{y"~.y,')dz,
we
obtain
(663)
c,+c^= ^^^'"~^''h
generalized so as to hold true of the formation of
new
any kind on
of (661) cal
of
any kind
if
be formed upon
the second
member
new matter
J. TF.
Gibhs
489
common
from the M'ant of absolute uniformity solids, and on account of the amorphous in the internal structure of are necessary to bring which processes passive resistances to the
tions are very great, principally
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
Let us apply the same method to the case The surface between the solid and a crystal.
of plane portions, the directions of which
which the
solid is
fluid will
now
consist
may
be regarded as invarisome
of pieces of ice.
Proceedings of
vol. xxi, p.
vi'hich
Royal
Society, vol. x, p.
440
ser.,
146.)
Although
is
this is a
body of
takes place
may
effect,
so
general character
is
concerned,
is
an isotropic
body.
we may
that the symbol relates to the surface between ice and water) for different orientations
of the axes of crystallization,
when
In
measured by a quantity
which
when one
of
and
to the
surface.
But under the circumstances of the experiment, since we may two systems of axes having precisely the same directions,
is
evidently not
suffi
tendency of pieces of
faces
when meeting
case
of
ffn
and
It vdll
in
With
Royal Society
407.
490
able.
J.
W. Gibhs
If the crystal
I'
cot
oo') SJST,
where fy' and fy" denote the volumedensities of energy in the crystal and fluid respectively, s the area of the side on which the crystal grows, (1) the surfacedensity of energy on that side, s(i) the surfacedensity of energy on an adjacent side, go' 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
incre
ments of entropy and of tbe quantities of the several components will be represented by analogous formulas, and if we deduce as on pages 485, 486 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 expression
equal to zero,
we
condition of equilibrium
{es'tn.'li,"y,'+p")s6N
+ :^"
where G and
the preceding formula.
0' /'
cosec Gj'(f
I'
cot
go')
6N=
fg.^,
0,
(G64)
fsd)' i"
same
sides as
and
This gives
/'.
= fy'
7k'
{ p"
vr^^
'2'i a'
I'
cosec
go
gV cot go'\
(')
is
jy'
It
will be
small or narrow,
we may
which
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 equililirium
is
ing some other body, the condition of equilibrium for the crystalline
foim
is
/rfifi^
shall
have the same value for each side of the crystal. any side of the crystal is meant
s aie
value
when
G and
first side.)
similar crystals
this condition, as
mea
J.
W. Gihbs
491
be
preceding equation.
If
we
of the areas of
its
value of c, the numerator and denominator of the fraction (666), multiplied each by 6N, may be represented by 6^{gs) and (3v
respectively.
The value
of the fraction
is
d2{o' s)
dv
as determined
sides
tal
aie fixed.
by the displacement of a particular side while the other The condition of equilibrium for the form of a crysis
that the
value of this differential coeflicient must be independent of the particular side which
supposed to be displaced.
s)
Foi a
constant volume
has therefore a
is
minimum
value
when the
condition of equilibrium
directly.
satisfied, as
may
easily be
proved more
When
^{o's)
crystal,
indefinitely
work required
in
to
and the
coeflicient of s
resents the
work gained
We may
W^
and
\J.e., ^'((Ts)],
Wy
the
work gained
in
the surfaces.
Equation (664)
may
then be written
(667)
6Wy+l:{0 6s)z::zO.
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 o' in all the sides were supposed to diminish in the
same ratio as the linear dimensions of the crystal. W^s, would then be determined by the relation
The
variation of
d TFs =
and that of
d:^{ff s)
= I 2{0 ds),
Wy by
(667).
Hence,
dW^=^dWy,
492
J.
W. Gibhs
TTs TFv
= iWs==iTFv,
(668)
the same relation which we have before seen to snbsist with respect
to a spherical
mass of
425, 465.)
The equilibiium of the crystal is unstable with respect to variations when the surrounding fluid is indefinitely extended, but it may be made stable by limiting the quantity of the fluid. To take account of the influence of gravity, we must give to yUj" and p" in (665) their average values in the side considered. These
in size
coincide
(when the
with
The values of
gravity
is
concerned.
Now
since
by
and
we have
Comparing
(664),
we
crystal will have the greater tendency to grow, (other things l)eing
equal,) according as the crystal
is
When
on
two masses
may
we
be neglected.
is
regarded as
in
a state of
and tempera
make
the
d(r,'^i,"p")
dz
Q^
is
determined
in
accord
dp))t,m
}//'
is
equivalent to
(669)
{X =J_. \drn^Jt,p,m
y^'
*
suffixed
is
used to represent
coefficient.
all
etc.,
except such as
may
J.
W. Gibbs
493
or
The tendency of
a crystal to
fluid,
be greater^in the
upijei*
Again, we
may suppose
the
fluid
and
will
its
The temperature
z.
then
is,
with
We
may
same crystal
These condifluid is
by the
fluid
in
gently stirred.
Owing
?/v'
we cannot
their
if
regard
fy'
and
in
we may regard
Therefore,
=.
t dti^'.
we
make
no
?;v'
foi'
the
mean temperature
may
treat
t
t/y'
as constant.
We
shall then
effect of
gravity shall
vanish
dz
which
dp Jii,m~ ^i"
or,
by
(90),
i^)'
Since the entropy of the crystal
is
=^.
(670)
sure
is
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
The manner
paragraph.
This
is
when the
crystal
is
growing
consider
or dissolving rapidly.
When
it
is
ably supersaturated, the action of the crystal keeps the part immediately contiguous to
The
flixid,
and
will
The same
S.
453
Wiedemann's
Bd.
ii,
S. 1.
494
J. TF.
Gibbs
supersaturated
only so
at
much
as
is
grow
all, it is
not to be
value (or
s)
has a
minimum
may
body supporting the crystal) will always be the 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 continuous as condensation or evaporation between a liquid and gas, or the
fluid.
(664)
intended unless
6N
is
we can only
con
clude with certainty that sensible changes cannot take place for
equilibrium
may
to evaporation,
is
explained (see Clausius " Ueber die Art der Bewegung, welche wir
Fogg. Ann., Bd.
c, S.
Warme
is
nennen,"
353
XIV,) by supposcontinually
ing that a passage of individual molecules from the one mass to the other
may
many
between amorphous
fluids,
The same supposition may be applied, at least solids and fluids. Also in the
there
may be
mass of
the solid.
would be
sufficient to
make
the probability
and
it
equilibrium that the theoretical conditions deduced above should be precisely satisfied.
But
this supposition
very small
side.
The following view of the molecular state of a crystal when in equilibrium with Since the molecules at respect to growth or dissolution appears as probable as any. the corners and edges of a perfect crystal would be less firmly held in their places
than those in the middle of a
theoretical equilibrium (6G5)
side,
we may
is satisfied
on each side
The boundaries
of these
b}
may
indeed attach themselves to the side of the crystal but they will speedily be dislodged,
and
if
J.
W. Gihhs
495
diiferent
solid.
If
we apply
it
is
evident that
to the surfaces, a
f^{GST)Dl
to
in (611),
definition of
in its
neces
be made good
greatly to affect the general smoothness of the surfaces, except near the edges
the sur