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TO
PHYSICS
AND CHEMIS'
BY
J.
J.
THOMSON,
M.A., F.R.S.
FELLOW OF TRINITY COLLEGE AND CAVENDISH PROF OF EXPERIMENTAL PHYSICS, CAMBRIDGE.
MACMILLAN AND
AND NEW YORK.
1888
CO.
PRINTED BY
C.
J.
CLAY, M.A.
&
SONS,
AT THE UNIVERSITY
PRESS.
PREFACE.
THE following pages contain the substance of a course of lectures delivered at the Cavendish Laboratory in the Michaelmas Term of 1886. Some of the results have already been published in the Philosophical Transactions of the Royal
Society for 1886 and
phenomena which belong
either entirely neglected
treatises
1887, but as they relate to to the borderland between
two departments of Physics, and which are generally
upon
either,
I
or but briefly noticed in have thought that it might
perhaps be of service to students of Physics to I have publish them in a more complete form. included in the book an account of some investigations
published after the delivery of the
lectures
which illustrate the methods described therein. There are two modes of establishing the connexion between two physical phenomena the most obvious as well as the most interesting of these is to start
;
with trustworthy theories of the phenomena in question and to trace every step of the connexion between
them.
This however
is
inglv limited
number of
cases,
only possible in an exceedand we are in general
may
a
be,
they must be related to each other in such
way
that the existence of the one involves that
of the other.
It is
the object of this
of
applying general
book to develop methods dynamical principles for this
purpose.
have adopted (of which that used the book was suggested by Maxwell's paper on the Electromagnetic Field) make everything depend upon the properties of a single
I
The methods
first
in
the
part
of
function of quantities fixing the state of the system, a result analogous to that enunciated by M. Massieu
and
Prof. Willard
Gibbs
for
thermodynamic pheno
paper on the "Equilibrium of Heterogeneous Substances" to the solution of a large number of problems in
applied
mena and
by the
latter in his celebrated
thermodynamics. I wish in conclusion to thank
my
friend
Mr
L. R.
Wilberforce, M.A., of Trinity College, for his kindness in correcting the proofs and for the many valuable
suggestions he has
made
while the
book was passing
through the
press.
J.
J.
THOMSON.
TRINITY COLLEGE, CAMBRIDGE,
May
ind, 1888.
..... CHAPTER III.. CHAPTER Preliminary Considerations I..CONTENTS. i CHAPTER The Dynamical Methods to be II. Temperature upon the Properties of Bodies CHAPTER VII. .. Electromotive Forces due to Differences of Temperature CHAPTER VIII. Application of these Principles to Physics CHAPTER IV. employed . Discussion of the terms in the Lagrangian Function CHAPTER V. the Systems CHAPTER Effect of VI. when . Reciprocal Relations between Physical Forces exerting them are in a Steady State .
mean Lagrangian Function . . . . . Effects produced by Alterations in the Physical Conditions on the Coefficient of Chemical Combhiation. . . 179 CHAPTER Dissociation XIII.Introductory to the Study of Reversible Scalar Phenomena . ... XVII. 193 CHAPTER General Case of Chemical Equilibrium XIV. 243 CHAPTER The Connexion between Change Electromotive 265 . .... 140 CHAPTER Calculation of the X.. . Force and Chemical XVI.. 233 CHAPTER Change of State from Solid to Liquid . . . . 158 CHAPTER Properties of Dilute Solutions . . . XII..215 CHAPTER XV.. . 151 CHAPTER Evaporation XI.
until the researches of Davy. CHAPTER I. Rumford. the development of the Kinetic.APPLICATIONS OF DYNAMICS TO PHYSICS AND CHEMISTRY. IF we consider the principal advances made in the Physical Sciences during the last fifty years. PRELIMINARY CONSIDERATIONS. i. we shall find that one of their most conspicuous effects has been to intensify the belief that all physical phenomena can be explained by dynamical principles and to stimulate the from Mechanics This belief which search for such explanations. Mayer and others showed that the kinetic energy possessed by bodies in visible motion can be very readily rnriTrprtPrl into 1^pa^ Tnillp rrmr/=>nxri=v nrnx?^/! tliaf ttrlie>nenrov .. Theory of Gases. such as the extension of the principle of the Conservation of . is the axiom on which all Modern Physics is founded has been held ever since men first began to reason and speculate about natural phenomena. the discovery of the Induction of Electric Currents.Energy to Physics. it remained unfruitful Joule. but. with the remarkable exceptions of its successful application in the Corpuscular and Undulatory Theories of Light.
Berlin. and the invariable relation between the quantities of heat produced and of kinetic energy lost. or of Vis. The case which from its practical importance at first attracted the most attention was that of the transformation of heat into other forms of energy and vice versa.of kinetic energy into heat conphilosophers that heat itself is kinetic energy. In this case it was soon seen that the principle of the . Helraholtz. These conceptions were developed by several mathematicians but especially by v. holds in the transformation of heat into kinetic energy and vice versa.Viva it was then called. who. in his treatise Ueber die Erhaltung der Kraft. are really forms of kinetic energy though the moving bodies which are the seat of this energy must be indefinitely small in comparison with the moving pieces of any machine with which we are acquainted. showed that The ready conversion these vinced as the principle of the Conservation of Energy. 2. This discovery soon called attention to the fact that other kinds of energy besides heat and kinetic energy and can be very readily converted from one form into another. this irresistibly suggested the conclusion that the various kinds of energy with which we have to deal in Physics. 1847. applied the method of the Conservation of Energy to the dynamical various branches of physics ciple and showed that by this prin many wellknown phenomena are connected with each other in such a way that the existence of the one involves that of the other. such for example as heat and electric currents.
take place in the body. and Sir William Thomson on the "axiom" that it is impossible by means of inanimate tion of matter material agency to derive mechanical effect from any porby cooling it below the temperature of the coldest of the surrounding objects. hut that these relations could be deduced by the help of another which states principle. Thus we could not expect that for the dynamical treat ment of Physics the principle of the Conservation of Energy . the integration being extended over any complete cycle of operations. founded on various axioms by different example Clausius bases it upon the "axiom" that heat cannot of itself pass from one body to This statement thus is physicists. a dynamical method and in general is not sufficient by itself to solve completely any dynamical problem.certain changes. the Second Law of Thermodynamics that if when to a system where then all the actions are perfectly reverat the sible a quantity of heat dQ be communicated absolute temperature 0. We might have expected a priori from dynamical considerations that the principle of the Conservation of Energy all would not be sufficient by itself to enable us to deduce the relations which exist between the various properties of For this principle is rather a dynamical result than bodies. Thus the Second Law of Thermodynamics is derived from experience and is not a purely dynamical principle. for another at a higher temperature.
before we can translate them quantities we wish to and so require further knowledge in terms of the physical such as intensity of measure. while for this case the other method degenerates into the principle of the Conservation of Energy.been we possess other methods. The object of the following results to see what pages is to endeavour can be deduced by the aid of these purely dynamical principles without using the Second of Thermodynamics. or velocity. Law The advantages of this method in comparison with that of the two laws of Thermodynamics are (1) that it is a dynamical method. 3. the results are expressed in terms of dynamical quantities. (3) that the method can be applied to questions in which there are no transformations of other forms of energy from or into heat (except the unavoidable ones due to friction). since the a dynamical one. and so of a much more fundamental character than that involving the use of the Second Law. Fortunately Hamilton's principle of are applied than the Conservation of Energy itself and yet are capable of completely determining the motion of the system. The disadvantages of the method on the other hand are that. which hardly require a more detailed knowledge of the structure of the system to which they tried. such as Varying Action and the method of Lagrange's Equations. such as energy. which is often not sufficient to solve the problem. is method momentum. (2) that one principle is sufficient instead of two. a .
wmuu ^tumui UK mcabLueu. none of these proofs seem quite satisfactory . j_.uuia. it might unpromising undertaking to attempt to to we have apply dynamics to such systems. that the object of this application But we must remember is not to discover the properties of such systems in an altogether a priori fashion. but even if the connexion it an unexceptionable way would still had been proved seem desirable in to investigate the results of applying the principle of Least Action.r . but rather to predict their behaviour under certain circumdanrpc: nftpr hflvinor nhsprvprl . If these results agree with those obtained by the use of the Second of Thermodynamics. For reason there are some cases where the Second Law of Thermodynamics leads to more definite results than the dynamical methods of Hamilton or Lagrange. directly to various physical problems. it will be a kind of practical proof of the connexion between this law and the principle of Least Action.a.uiy. 4. Many attempts have been made to show that the Second Law of Thermodynamics is a consequence of the principle of Least Action . or the equivalent one of Lagrange's Equations. this in me i rnybujtu. structure of the bodies which form Law most of the dynamical systems with which seem a somewhat deal in physics. as they show what part of these problems can be solved by dynamics. and what has to be done by considerations which are the results of experience. Considering our almost complete ignorance of the 5.i.it nnrlp. Even here I venture to thinlc the results of the application of the dynamical method will be found interesting.
say. and we can do this even though position of B we are ignorant of the nature of the mechanism connecting find that the motion of extent if the two pointers. B. now we observe how the velocity and position of B depend on the velocity and position of A. the This tions illustrates may enable us to branches of physics. A may happen that we set another one. suppose we investigate experimentally the effect of a current of electricity both steady and variable upon the torsion of a longitudinally . we can by the aid of dynamics foretell the motion of A when the velocity and are assigned. is assigned when that of in which dynamical consideraconnect phenomena in different For the observation of the motion of way B may be taken to represent the experimental investigation of some phenomenon in Physics. it If Then if we move one of the pointers. while the deduction by dynamics of the motion of when A A assigned may represent the prediction by the use of Hamilton's or Lagrange's principle of a new phenomenon which is a consequence of the one investigated experithat of is B mentally.behind the dial the various pointers are connected by a quantity of mechanism of the nature of which we are entirely ignorant. Thus to take an illustration. in motion. Or again we may to some B when A is assigned depends velocity and position of a third pointer C\ upon the case^ve in this observe the effect of the motion of C upon that of A and we may deduce by dynamics the way in which the motion of C will be affected by the velocities and positions of the pointers B A and B.
principle the motion of A when that of more general case which we have to consider in Physics is A moves in B when instead of two bodies attracting each other we have two phenomena which mutually influence each other. . as when we have two bodies each other if we observe the motion of A B which results when a known way we can deduce by the aid of this The is known.The method is really equivalent to an extension and generalization of the principle of the equality of action and and J3 acting upon reaction.
its detection. the existence function. now for convenience of reference collect the dynamical equations which we shall most frequently have to shall We use. 6. they reduce the subject to the determination of this In general the way that we are able to connect various physical phenomena is by seeing from the behaviour of the system under certain circumstances that there must be a term of a definite kind in this function. methods which do not require an intimate knowledge of the system to which they are applied. . The methods introduced by Hamilton and Lagrange possess this advantage and. of this term will then often by the application of Lagrangian or Hamiltonian methods point to other phenomena besides the one that led to 7. As we do not know the nature of the mechanism of the physical systems whose action we wish to investigate.CHAPTER II. as they each make the behaviour of the system depend upon the properties of a single function. THE DYNAMICAL METHODS TO BE EMPLOYED. all that we can expect to get by the application of dynamical various properties of principles will be relations between And to get these we can only use dynamical bodies.
and q a coordinate of In this case f and /. which may be derived from equation (i) (Routh's Advanced Rigid Dynamics.V tending to increase q. p. In the following pages the term thenic tions " " speed coordinates " will for the sake of brevity be used . are each supposed to be any typewhere constant. t the time. In many cases however instead of working with the velocities corresponding to all the coordinates it is more convenient to work with the velocities corresponding to some coordinates but with This is the the others. Part n. especially convenient momenta corresponding when some to of the coordinates only enter the Lagrangian function through their differential coefficients and do not themselves occur explicitly in this function. In a paper On some Applica" of Dynamical Principles to Physical Phenomena (Phil. 1885. T V In some cases it is it form but in others is convenient to use the equation in this more convenient to use Lagrange's Equations. Trans. V ^ 2 '' ~dt~dt~~dq L is written for function and Q is and is called the Lagrangian the external force acting on the system T.) I have called these "kinos" coordinates. In the preceding equations the kinetic energy is supposed to be expressed in terms of the velocities of the coordinates.and are respectively the kinetic and potential energies of the system. 249) and which may be written in the form d dL where dL = . .
(Stability of Motion to method which enables us coordinates der. . .. x is dLjdx... d$. have a series of equations of the type d dL ' dL' _ ...&C.then Routh has corresponding to the coordinates <$> 1} s shown that if we use instead of Z the new function Z' given by the equation. 4) d<^ i d$ 2 and eliminate ^.. The method as follows : suppose < that we wish to use the velocities of the coordinates q^ ^a . . since dL * acts : we have by Lagrange's equation since no external on the system r force #^ =0 as the tion d dL .For if x be a speed coordinate. dT dT r L =L ~^m~^^r~^ c . ^ _ cp 2 .. (3) momentum Routh corresponding to constant.by means of the equations = dT . p. 61) has given a general use the velocities of some i and which and the momenta corresponding to the remainis applicable whether these latter coordinates is are speed coordinates or not..d$: = *. .. . this equa shows that it is 8..and the momenta . . * _  dT . we may Thus we then as far as the coordinates q^ ps are concerned use Lagrange's equations if we substitute Z' for Z.
of these three things. We see however that to when we calculate the 'energy" corresponding any physical condition the interpretation may be ambiguous if the energy is not entirely potential. Thus to said that the energy of a piece of where k iron. and smce this function completely determines the motion of the system it is all we require for the investigation of its properties. throughout which the intensity 2 of magnetization is uniform and equal to /. 9. And without further considerations o we do not know whether this represents an miinnf r\f VinAfir> pnprcn? T^lofs nr nnfpntial pnprmr T^ltl' . is . modified form and this So that the term in the energy which we have cal culated may be any one take an example. is the coefficient of magnetic induction of the but all that this means is that the term I 2 j2k occurs in the Lagrangian function (modified or otherwise) of the system whose motion or configuration produces the phenomenon of magnetisation.J J2k.the part of the kinetic energy corresponding to the coordinate </>! then we see by (4) that Z' = the kinetic energy of the system minus eliminated. its potential energy minus twice the kinetic energy corresponding to the coordinates whose velocities are that If we do not know the structure of this system all we can determine by observing its behaviour will be the Lagrangian function or its modified form. it is soft iron of unit volume. For what we its really calculate is is the Lagrangian the kinetic energy minus the potential energy mimes twice the kinetic energy corresponding to the coordinates whose velocities are elimifunction or nated.
j possess a quantity of potential energy Mij where. kiuosthem'c or speed coordinates < i.< OT Let cnnnnsp tlinf tViprp nrp rin tprms in flip .io. the system completely in this case whenever function it ims amoiguHy now ever aoes not occur n we nave mapped out by coordinates. the volume by considering the mechanical forces between two circuits carrying electric currents. that is. n. Two investigations in the second volume of Maxwell's Electricity and Magnetism afford a is good illustration of the way in which this ambiguity cleared away by an increase in the precision of our ideas In the early part of about the configuration of the system. it is circuits shown that two such conveying currents i. coordinates which explicitly. in the expressions for the kinetic or potential energies. or may be the momenta corresponding to them. < 2 . because we find a term in the Lagrangian must be expressed it in terms of these coordinates and their velocities.Mij units of potential energy really possesses + Mij units of kinetic.. q a . and \ve can tell by inspection whether the term expresses kinetic or potential energy... qv occur Suppose that we have a system fixed by n coordinates./!/ is a quantity depending on the shape and size of the two circuits and their relative position.qn of the ordinary kind... and no m fnrlVi<=>r shall call positional coordinates. The following considerations may be useful as helping to show that this ambiguity is largely verbal and is probably mainly due to our ignorance of what potential energy really is. and which we . Later on however when coordinates capable of fixing the electrical configuration of the system have been introduced it is shown that the system instead of possessing ..
....... L M??)~ MM")' the kinetic energy arising from the motion of the q or positional coordinates. or........for the q coordinates if instead of the ordinary Lagrangian function L which reduces in this case to the kinetic energy we use the modified function L' given by the equation L'=L^ a<j> ..... n < 2 are to be eliminated by the aid of the Thus since the expression for L does not contain any terms involving the product of the velocity of a q and a <j> will be of the form coordinate..dT .dT and where equations < ... .... N (7)...... modification of the Lagrangian equations ( T( } but so that equation (8) reduces to d dT dT .. where T (ff) is By Routh's we have di do .... (6).. . T($$) that arising from the motion of the kinosthenic or speed coordinates......
. equations of motion would d dt dT d(} dV =_ ^ _ dl^ ay dq } (10). the configurations of these systems being capable of being fixed by kinosthenic or speed Thus from this point of view all energy is kinetic. exactly like a system potential energy is is T (qq \ and whose T(^ Thus we may look on as kinetic energy arising the potential energy of any system from the motion of systems con nected with the original system coordinates. the only thing doubtful being whether the kinetic energy is due to the motion of ignored or positional coordinatescan however be determined at once by inspection. x 1 system By comparing equations (9) and (10) we see that the fixed by the positional coordinates q will behave whose kinetic energy .have been ot the type. and all terms in the Lagrangian function express kinetic energy. 12. this Some of the theorems in dynamics become very Let us take for simpler from this point of vieAv. example the principle of Least Action that for the uncon much strained motion of a system whose energy remains constant Tdt minimum from one configuration to another and apply it to the system we have been considering in which all the energy is kinetic but some of it is due to the motion of a is a system whose configuration can be fixed by kinosthenic coordinates.
to more than embody the results of experiments in a form suitable for mathematical investigations.system will it will take by its unguided motion go along the path which from one configuration to another in the least possible time. the systems. in many cases we should expect it to be mainly the ether. The material system must of course include whose motion produces the same effect as the potential energy of the original system. or the surrounding ether. This view which regards all potential energy as really kinetic has the advantage that it is of keeping before us the idea one of the objects of Physical Science to explain phenomena by means of the properties of matter in When we have clone this we have got a complete physical explanation of any phenomenon and any further natural motion. and two configurations are not supposed to coincide unless the the kinosthenic systems configuration of these kinosthenic systems coincide also. may be either that of parts of the system. does little sense of the term. which we regard as the potential energy of the "f" systems. The matter whose motion constitutes the kinetic energy " <" of the kinosthenic systems. . It explanation must be rather metaphysical than physical. not so however when we explain the phenomenon as due to changes in the potential energy of the system for potential is . energy cannot be explain said. in the strict It anything. or both .
and magnetism and the way in which these depend upon the motion and the configuration of the bodies which exhibit the phenomena. be well to begin with the cases IN our applications of Dynamics to Physics it will which are the most nearly we consider in ordinary Rigid Dynamics. Reversible scalar phenomena. 13.CHAPTER III. We shall begin phenomena in elasticity. electricity. Irreversible 3. as temperature is prominently involved lastly we shall consider irreversible Thus the order in which we shall consider the effects. Reversible vector phenomena. phenomena. subject when there is no friction all the motions are reversible and are chiefly relations between vector quanallied to those Now in this We shall therefore begin by considering reversible tities. These phenomena differ from some we shall consider . example in which a scalar quantity such : subject will be 1. APPLICATION OF THESE PRINCIPLES TO PHYSICS. 2. vector effects and afterwards go on to reversible effects those for involving scalar as well as vector relations . by considering the relations between 14.
for example. In the applications of Dynamics to Physics however. term "coordinate" than that which obtains There a coordinate is a geometrical quantity helping to fix the geometrical configuration of the system. the configurations of the systems we consider have to be fixed. while we may feel pretty sure that the coordinates which we use to fix the configuration of the system with respect to may to fix it as far as many of its we can . physical properties. are not sufficient to is fix it in fix it every detail if that they would not be sufficient of observing differences we had the power .and the saturation of magnets may impose). do when we wish to apply 15. with respect to such things as distributions of electricity and this magnetism. The the other hand depend upon a multitude of coordinates over whose individual motion we have no control though we have some over their average motion. dynamical methods to investigate the motion of a system is to choose coordinates which can fix its configuration. as well as geometrically. though they observe it. We shall find it necessary to give a more general thing we have The meaning in to the ordinary Rigid Dynamics. As the first kind of phenomena most closely resemble those material other phenomena on we have to do with first in ordinary dynamics to we shall begin with them. Again the coordinates which fix the configurations of the systems in ordinary dynamics are sufficient to fix them completely. and to do we have in the present state of our knowledge to use quantities which are not geometrical.
as for example when . if fh then If all 8 Jto L'dt=o when is (IT). vol. cal Society. the kinetic energy vanishes coordinates q^ .. and we may treat the system as if it were fully determined differential coefficients is by the coordinates in terms of whose the kinetic energy expressed. though it infinite number of coordinates to fix the configuration of the fluid completely...$ 1} $ 2 the momenta corresponding to these coordinates 2 . i. when a sphere fluid. that is q^ $. modification of the Lagrangian function. as the positional the case when a number of there is solids move through a perfect fluid in which difference between the If no circulation. (Proceedings of London Mathemati173) has proved that if Z' be Routh's being the coordinates retained.. and Tait (Natural Philosophy. xv. those ignored.trations of this latter point moves through an incompressible For example.. L' is the kinetic and potential energies of the system. < < Q Q respectively. 1} 2 . And again Larmor p. Now Thomson p.. however the kinetic energy does not vanish when the velocities of the positional coordinates all vanish. we can express the kinetic energy of the system comprising both sphere and fluid in terms of the differential coefficients of the three coordinates which fix would require a practically the centre of the sphere.... are constant. 320) have shown how we can "ignore" these coordinates that when the kinetic energy can be expressed without them.
. that is. we might feel uncertain whether the symbol representing the intensity of a current was a coordinate or The simplest dynamical the differential coefficient of one. then the symbol is a coordinate. as the intensity of a current flowing through ... considerations difficulty. Let us apply these considerations to the example mentioned above . Thus we see that we may We shall take this as our definition of a coordinate. introduce a symbol to fix a physical quantity we may not at first sight be sure whether it is a coordinate or the differential coefficient of one with respect to the time. we must have d j. the energy at the same time remaining constant. at aq . however if will enable us is Thus when there to overcome this no dissipation of energy by irreversible processes. then whatever these quantities may be. When we For example.and their first differential coefficients. the symbol represents a velocity. the differential coefficient of a coordinate with respect to the time. the quantity represented by the symbol remains constant under the action of a constant force tending to alter its value. if it remains constant and not zero when no force acts upon it... aq treat any variable quantities as coordinates if the modified Lagrangian... Again..( 12 j. there being no dissipation and the energy remaining constant. function can be expressed in terms of them and their first differential coefficients. a series of equations of the type dL' ~j~ dL' ~~j _ O.. 1 6.
z of the displacements of any small portion letters a. we shall use the letter w for this purpose. the components parallel to shall the axes of x. change of a coordinate and not by the coordinate Specification 17. (2) Coordinates to fix the configuration of the strains in the system. of the body. fix the geometrical configuration of any bodies of this purpose we shall use the coordinates ordinarily used in Rigid Dynamics and denote them by the letters x l} xz ^3 . It will be convenient to have a letter typifying these quantities generally without reference to any one in particular. to fix the position in space of finite size which may be in the system.. (1) use Coordinates to i. and when we want to denote a geometrical coordinate generally without reference to any one in particular we shall use the the system. g. /3.. a. y. letter x. For .e. . we shall use the letters f. b. tively. of Coordinates. c respectively. and denote them by the strains y respec For the da d]3 dy } dx' dy' dz fdy \dy dj!\ /da ' dy" dz) \dz e..the rate of itself. as is ordinarily on elasticity. To fix the configuration of the system so far as the shall phenomena we are considering are concerned we the following kinds of coordinates. We done in treatises use for this purpose.
We might do this by specifying the intensity of magnetization at each point.caus an electric displacement. This way of looking at it brings it into harmony with the two most usual ways of representing the magnetization of a body. even in the simplest case. According to Ampere's theory the magnetization to electric is due flowing through perfectly conducting In this case the circuits in the molecules of the magnets. one of which is a kinosthenic or speed coordinate. We shall denote the kinosthenic coordinate by and the geometrical one by 77 and suppose that they are so ordinate at chosen that the intensity of magnetization nrViova ic fVii= any point fViF> momentum r>ni"ri=cr\nnrliriar tr is >?. any magnet is built up of a large number of small magnets Here the momentum correarranged in a polarized way. of finite size According to the Molecular Magnet theory. Ampere's theory and the hypothesis of Molecular Magnets. differential coefficient of the kinosthenic fix currents coordinate would the intensity of the current. (4) Coordinates to fix the magnetic configuration. little magnet. viz. VinriefTipnir . which it is well fitted to do by constancy the other co little may be regarded as fixing the arrangement of the magnets in space. sponding to the kinosthenic or speed coordinate may be regarded as fixing the magnetic moment its of a . upon two coordinates. ana in a conductor tne rime integral of a current flowing through some definite area. and the other coordinate the orientation of the planes of the circuits. but it is clearer I think to regard the magnetic configuration as depending.
Having chosen me coordinates there are two ways which we may proceed. by experience we conclude that the term we are considering does not exist in the expression for the Lagrangian function. We can then by is applying Lagrange's equation to this term see what are the consequences of the specific inductive capacity of the dielectric We shall being altered by strain (see 39). Thus. we know by considering the amount of work required to establish the electric field that there must be in the Lagrangian function of unit volume of the dielectric a term of the form where and K the specific inductive capacity of the dielectric D the resultant electric displacement. and also because we shall have a great many examples of the second method later on since the scalar phenomena do not admit first of being treated by the first method. and then investigate the physical consequences of each term If these consequences are contradicted in this expression. make use of both methods but commence with the first as being perhaps the most instructive. Or we may know as the result of experiment that there in the expression for the must be a certain term Lagrangian function and proceed by the application of Lagrange's Equations to develop the consequences of its existence. for example. thing we have to . We may either write down the most general expression for the Lagrangian function in terms of these coordinates and their differential coefficients.in 1 8. In using the first method the 19.
which is the only part we can typify. or a velocity and involving the product of two velocities a momentum of two coordinates of different kinds. Again. There are five sets which are quadratic functions of the velocity or momentum corresponding to one kind of coordinate.and that we work with Routh's modification of the Lagrangian function. To exists or not determine whether any particular term of this type we must determine what the physical conseit quences of would be . if these are found to be contrary . The most general expression for the terms corresponding to the kinetic part of this function. is of the form + + + (se/o/) ob 8 + (7717) if + yjt () 2 2 2 (xy) 2 xy + 2 2 (xw) xw + 2 (xrj) cti] + (x) x+ (yw] yw 4 2 (yrj) yrj + 2 These terms may be divided into fifteen types. there are ten sets of terms of the type (xy) xy or (xg) xg. Each of these five sets must exist in actual physical systems if there is phenomena which anything analogous to inertia in the the corresponding coordinates typify.
. Thus the effect of the term (pq)pq is equivalent to the existence of a force of the type / equal to {(#>*} *{(*) that is.Lagrangian function of the type where/ and q may be any of the five kinds are considering.... (15).. {<#)/>  (#)^+sj(^)tf} and a force of type . v N where P is the external force of type/ acting on the system. a force of type q equal to KM *}!{<*) 4 that is.... of coordinates we Then we have by Routh's equations modification of Lagrange's d_d dt dp _d_ =p .............. dp . r equal to .. t}.
P
to
or
<!
Each of the terms in these expressions would correspond some physical phenomenon and as it is clearer to take a
suppose that p
is
definite case to illustrate this, let us
the
geometrical coordinate symbolized by x, and q the electrical coordinate y.
Then if the term (xy) xy occurred in the expression for the Lagrangian function, the mechanical force produced by
a steady current would not be the same as that produced by a variable one momentarily of the same intensity. This is
so because
by the expression
(14) there
is
the term
(xy)
y
there
in the expression for the force of type x, that is the mechanical force, and as y is zero if the current is steady, would be a mechanical force depending on the rate of
if this
variation of the current
term existed.
=
Again,
we
see from the term
(xy) y~ in the expression
cty
if (14), remembering that/ stands for x and q for y, that (xy) were a function of y the current would produce a
mechanical force proportional to
would not be reversed
reversed.
if
its square, so that the force the direction of the current was
Or again, if we consider the expression for the force of type y or q, that is the electromotive force, we see that the existence of this term implies the production of an electromotive
force
by a
body whose
(xy)
velocity
;
is
changing,
depending upon the acceleration of the body
this is
shown
by the existence of the term
x
in (15), the expression
one that would not be reversed when the direction of motio of the body was reversed. As none of these effects have been observed we concluc
does not exist in the expression for tr. Lagrangian function of a physical system (see Maxwei 574). Electricity and Magnetism,
that this term
21.
We shall now go
which involve the product of the
through the various types of tern velocities of two coorc
nates of different kinds, or a velocity of one kind and tl momentum of another, in order to see whether they exist
<
not in the expression for the Lagrangian function. The reasoning to be used is of the same nature as th
just given,
and we may
leave
it
to the reader to
show by
tl
consideration of the expressions (14) and (15) that tl existence of the several terms carries with it the coi
sequences

we
describe.
Taking the terms in order we have
1.
Terms of the form
(xy} xy,
We
have just seen that terms of
this
kind cannot exist
See also
7.
the expression for the Lagrangian function.
well, Electricity
2.
Ma
and Magnetism,
(xw)
n. part iv. chap.
Terms of the form
xiv.
Terms
of this form
may
exist in the case of
a vibrating sol
body which is also moving as a whole. For the velocity any point in the solid equals the velocity of the centre
gravity plus the velocity of the point relatively to
its
centre
3.
i
erms
01
me
torm
(xrj) xr,
that they would involve the existence of a magnetizing force in a moving body dependIt would also require ing upon the acceleration of the body. that the mechanical force exerted by a magnet should
cannot
exist, for
we can prove
depend upon the
rate
of change of the magnetization.
None
4.
of these effects have been observed.
Terms
of the form
(**)
*
apparently do not exist, for they would require that the mechanical force exerted by a magnet should depend upon
the rate of variation of the magnetic intensity, and this effect has not been observed.
5.
Terms of the form
(yw) yw.
would be possible to develop electromotive forces by vibration, and these forces would depend upon the acceleration of the vibration and not
If these terms existed
it
merely upon the velocity ; as these have not been observed we conclude that this term does not exist in the Lagrangian
function of physical systems.
6.
Terms of the form
If these terms existed there
would be electromotive forces
depending upon the the magnetic field.
TMiCktr olork
rate of acceleration of the changes in
rvm rrn/afi r>
fr\rr*&C!
inr1ir>o t o
rlotvoTMItnrr iirnm ^li**
y.
Terms
of the form
of this kind only involve the production of an electromotive force in a varying magnetic field, the electromotive force varying as the rate of change of the magnetic
Terms
field.
This
is
the wellknown
phenomenon of the producwhenever the
it
tion of an electromotive force round a circuit
number of
lines of
magnetic force passing through
is
changed. As the term we are considering is the only one in the Lagrangian function which could give rise to an effect of
this
kind without also giving
rise to other effects
which have
not been verified by experience, we conclude that this term does exist.
8.
Terms of
the form
(wtf) wrj.
we take any molecular theory of magnetism, such as Ampere's, where the magnetic field depends upon the
If
'
arrangement of the molecules of the body, we should rather expect this term to exist. The consequences of its existence have however not been detected by experiments.
If this term existed, then considering in the
its
first
place
effect
vibrating
upon the magnetic configuration we see that a body should produce magnetic effects depending
vibrations.
upon the
this
Secondly, considering the effects of
term on the strain configuration we see that there should be a distorting force depending upon the rate of
acceleration
affo/Mo
lio\rf>
of the magnetic
field.
IP
As
v>rs
hoon
i~J\ce>nrf>r1
tliova
neither of these CLtrlAm^^^ nf tl^n.
These would involve the existence of distorting
depending upon the rate of change of the magnetic and we have no evidence of any such effect.
10.
forces
field,
Terms
of the form
If
we assume Ampere's
is
term
hypothesis of molecule currents this of the same nature as the term (x) x which we
before, so that
discussed
unless the
properties
of these
finite size
molecular circuits
with which
21.
tions,
differ essentially
from those of
we
are acquainted this term cannot exist.
Summing up the results of the foregoing considerawe arrive at the conclusion that the terms in the
energy
Lagrangian function which represent the kinetic
depending upon the five classes of coordinates we are considering must be of one or other of the following types
:
(xx)
x'
(wiv)
i'
.(17).
We might make a model with five degrees of 22. freedom which would illustrate the connection between
these
types.
phenomena which
if
are fixed
by coordinates of
its
five
And
we arrange
the model so that
configuration
analogous to that possessed by the physical system, then the working of this model will illustrate the interaction of
phenomena in electricity, magnetism, elasticity &c., and any phenomenon exhibited by the model will have its counterin these subjects. part in the phenomena exhibited When however we know the expression for the energy
of such a model, there
order to see
is
how
it
will work, as
no necessity to construct we can deduce all the
it
in
rules
of working by application of Lagrange's Equations. And from one point of view we may look upon the method we are using in this book as that of forming, not a model,
the
but the expression for the Lagrangian function of a model every property of which must correspond to some actual
physical
phenomenon.
24. many The relations way we shall be between the phenomena in In this is physical able to electri magnetism and first elasticity. term we have to consider {xx} x 2 . THE LAGRANGIAN WE must now proceed to examine the terms in the expression (17) more in detail. and find what coordinates enter into the various coefficients (xx). 23. but we need not stop to consider the consequences of this as they are fully developed in treatises on the Dynamics of a System of Rigid Bodies. in a paper Next {xx} may involve the electrical coordinate y. be. for "On the Effects produced by the Motion of . (yy) When we have proved that these coordinates coefficients involve to some the particular we must go on will see what consequences obtain city. DISCUSSION OF THE TERMS IN FUNCTION. Avhich corresponds to the expression for the ordinary kinetic energy We know that {xx} may be a function of a system of bodies.CHAPTER IV. of the geometrical coordinate typified by x.
..... if the kinetic energy of an electrified sphere is the same as the mass of the body had been increased by 4/x<r/i5tf Thus whenever a moving body receives a charge of electricity its velocity will momentum is be impulsively changed. at the K being So the specific inductive capacity of the medium... to the original that the ratio of the increase in is mass mass. since the electric force surface of the sphere must be less than 75. The apparent increase in mass cannot exceed a very small quantity because air or any other dielectric breaks down when the electric force gets very intense. x " where <a is the radius of the sphere and /u. which is due to the "displacement currents" started in the surrounding dielectric by the motion of the electrification on the sphere. if it had mass.G.. which by (18) equal to . (18). The existence in the kinetic energy of this term. If we take 75 as the intensity in electrostatic measure in C..s. 1880)... the magnetic permeability of the dielectric surrounding it.. Dec.e a / o\ 15 a J \v . shows that electricity behaves in some respects very much For we see by the expression (18) that as.. we have..m+~ 2 1 * ... which is the value given by Dr Macfarlane Mag. and as the apparent mass suddenly increased the velocity must be impulsively will diminished.. units of the greatest electric force which a fairly thick layer of air can stand. for the remain constant.. (Phil.
using the same notation as before.. /i 2 1 15 5 lie \ (~m\ \2 If a ) J zr +2 i Ka ' v be increased by $v and is e by Se. the increment in the energy 15 a ) 15 a this Ka' must equal and by the Conservation of Energy QSe.we see that the ratio cannot exceed i . The is energy of the system. so that / z 4 [* \ 8 /j. l or about 4xio~ is /p. Thus pressure the alteration in mass.. so that 1 5 a ) 15 a Ka ^ ^  Z> Since no momentum mechanical force acts upon the system the will be constant. where p the mean density of the substance enclosed by the electrified surface. is only about 5 x io~ of the original of this term. mass. 6 x io~ 18 a?/m. and Let us much too small to be observed. now consider the electrical effects Let Q be the electromotive force acting on the sphere. even is if the 16 mean density inside the surface as small as that of air at the is atmospheric and oC. .
and the alterations in the velocity of such a point which occur during the day will produce a small diurnal variation in the capacities of condensers. When we have two spheres of radius a and a moving with velocities v and if respectively the kinetic " Effects produced by the energy (see the paper on the Motion of Electrified Bodies. If the earth does not carry the ether with it. is assuming Maxwell's 2 1 m+ 2 }V* 15 a ) is uA. .. 25.CDSo that the r capacity of the sphere i is increased in the ratio of to / i  2 i*.. April.Thus is increased in the ratio of i to i / i sphere p." Phil.2 m + \2 15 . R _ the distance between the centres of the two e spheres and . i + 'r}l/ a J $ ufl?'cose ^ where . but as the difference depends on the square of the ratio of the velocity of the condenser to the velocity of light it will be exceedingly small. 1881). Mag.Kv . or since according to the Electromagnetic Theory of Light ^K~ i V / s where V is the the capacity of the velocity of light through the dielectric. a point on the earth's surface will be moving relatively to the ether. the capacity of a condenser in motion will not be the same as that of the same condenser at rest. 2 / 4 & .' J ntffi the angle between their directions of motion.  g + u\ /I. theory. irT\a/fi \ra\ tr ili n TIT nocoe nnrl r^no vnroo c* /^f* +1* .
. show that these terms require the existence of the following forces on the two spheres. 4 fjie p. s those of the other. and we see that unless the two spheres move with equal and uniform velocities in the same direction the forces on the two spheres are not equal and opposite. ee' \ dx' . An attraction fj. since the sum of the actions and reactions is not constant but is a function of the accelerations. On a. COS along the line joining the centres of the spheres. A force '_ ^ee _ r . /fi. z' ( z are the coordinates of the centre of one sphere.equations in the way explained in 20. if being the accelerations of the spheres respectively. i> and . There are corresponding forces on the second sphere. j>. 71 3* in the direction opposite to the acceleration of the second sphere. The sum of the momenta of the two spheres will not increase indefinitely however. then 2 .ee' 3^' ^ VV . A force i . d f in the direction opposite to the direction of motion of the second sphere. the first sphere. We may (' easily prove that if x. y. d.ee' }dx 4 /x/ ju. y'..
AWCU is a icau LU the conclusion that the coefficient {xx} electrification of the system. x'. 85) the forces between two small electrified bodies in motion are the same as the term . are the coordinates of the centres of te. a function of the Thus according to Clausius' theory (Crelle. using the same notation as before. TV. if. y'. 1846. there was cos e  . w' the components of their velocities parallel to the axes of coordinates. we can see by taking the simple case when the bodies are moving same this straight line which we may take as the axis of In case the term in the kinetic energy reduces to . 82. vol. as in the x. The first of these been considering.13.U.20. This term leads however to inadmissible results. u'.VJ. the electrified bodies and v. The forces which according to Weber's theory (Abhandis the same as the term we have just lungen der Koniglich Sachsischen Gesellschaft der WisscnMaxwell's Electricity and Magnetism. n. p. 2nd in Edit. z. 211. v'. schaften. y. %'. motion may easily 853) exist between two electrified bodies be shown to be the same as those which would the term exist if in the Lagrangian function there was where x. ap ywj R _ ee KR in the expression for the Lagrangian function. unier electrical meuucs uct>iuc& J.
We see from the expression (22) for the kinetic energy of a moving conductor that if we have a number of conductors moving about in the electric field there will be a positive term . of Weber's theory was first pointed out by v. that is. the expression for the kinetic energy from the point of view of its bearing on electrical phenomena we shall see that it shows that if we connect the terminals If we regard of a battery to two spheres made of conducting material. p. p.zee IR since the coefficients of n and u " are each increased by half this amount. then one of the bodies at least will behave as if its mass were negative. easily see that this theory is open to the same objection as Weber's. Hence if we take e and e of opposite signs and suppose the electrifications are great enough to make zee'jR greater than the masses of one or both of the bodies.Wj} . exist between two moving electrified bodies may easily be shown to be the same as those which would p& exist if there were the term g {(U in  tt U') +(V 7/)' +(W. This is so contrary to experience that we conclude This consequence the theory cannot be right. Helmholtz ( Wissenschaftliche Abhandlungen. The in his which according to Riemann's theory. 326. it would make an electrified body We behave in some cases as 27. i. 647).KR can the expression for the Lagrangian function. the will depend upon their quantity of electricity on the spheres velocities. if its mass were negative. given posthumous work Schwere^ Elektridtdt und Magnetisforces mus.
dfi dy *" . And therefi the speed with which electrical oscillations are propagal across any medium will be diminished by the presence 1 molecules moving about in it.electrification. light true the result on the rate of propagation of light. the diminution being p portional to the square of the ratio of the velocity of molecules to the velocity with which light is propagat Thus if the electromagnetic theory we have been discussing has important bearing on the effect of the molecules of mat across the is medium. for the effect the strain has practically been to bring the matter formi the bar nearer to the axis. i. for let moment then it can see that {xx} may be a function of t us take the case when {xx} is t of inertia of a bar about an axis through its centi evident if We is the bar be compressed in the midc and pulled out at the ends that the moment of inertia vi be less than if the bar were unstrained. strain coordinates. .e. through da. 28. decrease in the potential energy produced by a gn since an increase in the potential enei corresponds to a decrease in the Lagrangian functii Thus the presence of the moving conductors is equivali to a diminution in the stiffness of the dielectric with resp to alterations in its state of electrification. Thus the moment of iner and therefore {xx} may depend upon the strain coordinati These coordinates will in general only enter {xx} throu the expression for the alteration in the density of the strain body. (23)r .
y i!f y\) y? ~^~ 2 (y y) y\y<> ~*~ } Let us take the case of two conducting electrical configuration circuits whose .8 / (T. ya . consider that part of the Lagrangian function which depends upon the velocities of the electrical coordinates. This however 29. fix the shape of the first and second It is evident that the kinetic energy must be expressible in terms of these coordinates. of the centre of gravity and the shape and situation of the the shape of the second circuit and its position first..is fixed by the coordinates j ]5 j/ 2 are the currents flowing through the circuits respectively. we shall leave as an exercise for the reader. for the only coordinates necessarv tn fix flip svstem whir. and by l 2 coordinates helping to circuits respectively. relatively to the fix Let us denote by x2 . where jp.h we have omitted are those fixine . Let us now the part denoted by \K.V] dt=Q that we shall easily find the presence of (23) in {xx} leads to the introduction of the socalled "centrifugal forces" into the equation of elasticity for a rotating elastic solid.e.x any coordinate which helps to the position of one circuit relatively to the other. i. This part of the Lagrangian function conveniently written may in this case be Now we can fix circuits if we have the geometrical configuration of the two coordinates which can fix the position first circuit.
otherwise there would be a force between the two circuits even though the current in one of them vanished. and also to the differential coefficient with respect to the coordinate along which the force is reckoned of a function which does not involve the electrical coordinates. i dN . We see from this expression that dLjdx. dM . If we write for a moment x instead of x 2 x l (a coordi nate helping to fix the position of one circuit relatively to the other) then by Lagrange's Equations we see that these terms in force tending to increase i the kinetic energy correspond to the existence of a x equal to dL . there is a force between the two circuits proportional to the product of the currents flowing through them. This corresponds exactly to the mechanical forces 1 which are actually observed This is induction caused bv a neirrlihnrmno quite consistent with the apparent diminution in the selfrirr. The quantities L and are by definition the coefficients of selfinduction of the two circuits. (16) the force tending to increase x is dM that is .nif when an alternating current . .these coordinates. and hence N we see that the coefficient of the selfinduction of a circuit is independent of the position of other circuits in its neighbourhood and is therefore the same as if these circuits were re moved By 1 . and dN/dx must vanish.
1. part iv. for the coordinate y we } have ' d dL _ __ _ dt dj> l dU _ ~ dy } _ Y .. l\JLL \^J.L\_lVl Ci. And the expression (26) gives the E. T T/ ^ where y. so that the effects on the electrical configuration of the first circuit. any of the four quantities L. M. . arising from the term same as would be produced by an external electromotive force tending to increase y equal to are the l (26). Magnetism. n. F. the external electromotive force tending to l increase y^ Now as we shall prove directly dL'jdy = o. y^ yz vary in value there is an electromotive force acting round the if Thus circuit through which the current y^ flows.O exert O V^WW O V. V^WHO. produced either by the motion of neighbouring circuits conveying currents or by alterations in the magnitudes of the currents flowing through is the circuits. is . and it is one which illustrates the Dower of the dvnamical method verv well. vol. This example given in Maxwell's Electricity and chapter vi. V 1J\^ ical forces which two circuits carrying currents are known to upon each other proves that the term Mj> } j> 2 exists in the expression for the Lagrangian function. M. Let us now go on to consider the effect of these terms electrical configuration of the on the two circuits. By Lagrange's Equation .
that in which no forces act upon the is particle. the aid of the principle of the Conservation of Energy alone. and that some other principle must be assumed implicitly in those proofs which profess to deduce these equations alone. 30.law of the induction of currents follows at once by the application of Lagrange's Equations. Similar reasoning will show that \yy\ cannot be a 31. and it is certainly series of not when the electrical systems consist of a conducting circuits. for if it were there . the principle of the Conservation of is Energy particle satisfied if the velocity constant whether the moves in a straight line or not. for if it were the coefficients of self and mutual induction would depend upon the length of time the currents had been flowing through the circuits. by means of the Conservation of Energy \yy] is There is no experimental evidence to show that a function of the electrical coodinates y. just been considering is dynamicequivalent to finding the equations of motion of a particle with two degrees of freedom when under the action The problem we have ally know that these cannot be deduced by of any forces. And of in any case it would require the existence of electromotive forces which would not be reversed if the direction all the electric displacements in the field were re versed. for to take We the simplest case of all. function of the magnetic coordinates. From to this analogy we see that when we have two is circuits the principle of the sufficient Conservation of Energy not deduce the equations of motion.
for as we shall endeavour to show when we consider electrical resistance this effect might have been due to another cause. The evidence of various experimenters on this point somewhat conflicting. p. p. p. 404) on the other hand was unable to detect any such effect. de Chim. we see at once that it would indicate that the elastic properties of a wire would be was passing through it. 610. of self If it is then the coefficients circuits and mutual induction of a number of state of strain of the wires must depend upon the circuits. ( that the elasticity of a wire when is a current passes through it and that this not due to the heat generated by the current. 403) is and Tomlinson have observed diminished diminution Streintz n. Both Wertheim {Ann. Wiedemann's Elektricitdt. Then again. [3] 12.of the strain coordinates or not. 323. p. u. Wien. Wiedemann's Elektricitdt. Ber. forming the This result though not impossible has never been it is detected. if we consider what the effect on the elastic properties of the substance would be if {yy} were a function of the strain coordinates. To sum up we see that {yy} is a function of the geometrical coordinates but not of the electric or magnetic . [2] 67. But even if this effect were indisputably established it would not prove rigorously that {yy} is a function of the strain coordinates. altered while an electric current is et de Phys. and contrary to Ampere's hypothesis that the by a current depends only upon its strength and position and not upon the nature or state of the force exerted material through which it flows.
(28). In order to begin with as simple a case as possible 1 all the magnetic changes take place inde in this case we may neglect the term and confine our attention to the terms or as it is more convenient to write them Let us take parallel to first the case when the magnetization one of the axes. there is in tl Lagrangian function for unit volume of a magnet the term HI. us suppose that nitely slowly . The investigation in if  ... Thus the terms we a Lagrangian function of ur volume of a substance are those we have denoted by about to consider in the we may have in addition to these terms' arising from tl potential energy. Magnetism....... where by definition H us deno tl f=rf ..........electrical or strain coordinates. shows that 389 of Maxwell's Electricity at we suppose that all the energy ... and let the magnetic force parallel to this direction by and intensity of magnetization by /. x for example. the magnetic field is resident in the magnets... .
or in our notation and this is the term we previously denoted by itf}* Since the magnetic changes are supposed to take place indefinitely slowly. then the investigation in 635 of the Electricity and Magnetism shows that the Lagrangian function of unit volume anywhere in the magnetic field contains the term where B is the magnetic induction.but we have seen in determined left in this : manner 9 that the question whether energy is kinetic or potential is really is unsettled exists in the what is actually proved Lagrangian function. These two ways of regarding the energy in the magnetic field lead to identical results. Lagrange's equation for the t] coordinate reduces to . that the energy is that a certain term If we suppose distributed throughout the whole of the magnetic field. and as we shall for the present confine our attention to the magnetized substances we shall find it more convenient to adopt the first method of looking at the question. including unmagnetized substances as well as magnets. have seen that the Lagrangian function for unit volume of a magnet contains the term We HI.
The mechanical force parallel to 34. is constant. by its help. ff. acting on unit volume of the magnet is ' the axis of x dL' . so 23.and this since is supposed to remain constant and therefore %dr\ = dl. may be written So that if k be the coefficient of magnetic induction and defined by the equation we have by (31) I=3> and therefore (33). Lord Rayleigh that is 1887) has shown II H Mag. The relation between /and H'v$> however in general so complicated that there seems but little advantage to be gained by taking some empirical formula which connects the two and determining (Phil. A p. If we know the way in which / varies with H we could by this equation express A as a function of 7. For small values of 225. by equation (33) A in this case also constant.
35. the consequences of which are as is well known in harmony with Faraday's investigations on the way in which paramagnetic and diamagnetic bodies move when placed in a variable magnetic field. We assume that there is no torsion in the bar. p. 70. IT. produced by a magnetic investigate we shall now proceed it. g be the dilatations shall at present of the bar parallel to the axes of x. We have just investigated the mechanical forces field . shall We suppose that the changes in the strains take place so slowly that we may neglect the kinetic energy arising from them. f. Let e. The potential energy due to these strains is . to some of the stresses produced by Let us take the case of a cylindrical bar of soft iron whose axis coincides with the is axis of x. y. vol. and suppose that it magnetized along its axis. These are the same expressions for this force as those given in Maxwell's Electricity and Magnetism.1 dx . z respectively. also be written mechanical force parallel to the axis of x This expression may 2 k^dx with similar expressions for the components parallel to the axes of y and z.dH or and this is the acting on unit volume of the magnet.
dftjdy. hence by equatii a function of the strains. dL at the boundary. p. g respective! tl get the following equations by equating to zero variation caused by changing a into a + Sa d_L ~dx inside the bar. in. ==0 ' . 70 j) have shown that depends upon the strain in the magnet. and substituting da/dx. . dy/dz for e. We shall pi (32) A will be of ceed to investigate the stresses which arise this. Using the Hamiltonian principle in consequen t. __ we d dx d_L de _ ~ .neglecting those depending on the rate of variation 01 the assume to be indefinitely sma quantities which rate we shall The experiments of Villari and Sir William Thomsi (Wiedemann's Elektricttat. zero the variation caused by changing By equating to into /? + 8/3 we get dL _d_d dy inside the bar. f. dy df ^i) dL = af (38) at the boundary.
.. and it is shown in Maxwell's Electricity and Magnetism^ 642.dH JfT dH kff jaz or kHj.T p 4Uaro o m ]rn^. or z explicitly the terms H The first and second terms in the equations (35).o o f r O i V.I. (37) and (39) may conveniently be considered separately... Since L dL dx' reduce to dL ~d~y' dL ~ds .dff . respectively.." being the magnetic "a B induction.. that this distribution of force would strain the body in the same way as 2 hydrostatic pressure ff /Sir combined with a tension BPll^Tr along the lines of force. =* . These are the expressions for the components of the mechanical force acting on the body..dzT s . c . ...dL inside the bar d dL ~dk.dH ..m Tf a that the strains arising f rf o vo f 1. f....... ^ r is the only quantity in the expression for which can involve the coordinates x....nrr> Thus we may suppose +Q. (39) dL ^ at the boundary. dx dH kH dH ray . Ano.. y.
n df m+n d yn nde^ is ndf 5.111 rj I d dg we get d .. . ^ m n(d. . ?de ' <IA m(e' f #dA_ 'df J Solving these equations and putting 2. . . The dilatation <? equal to .DYNAMICS. ' yn . reduce to yn n de ^ ' m 3/ n d + 2/ . r^ > dg (^)l ) d symmetrical about axis If the magnet is its we have /=<and So that equations (42).
and equations (46) may be written i dl / de dk\ / m ~ dl )\yn n kl de dl \ . dl ' de (47). be altered by and constant magnetizing force in order to compare the formulae with the results of experiments \ve shall find it 2 more convenient to express de/dl dfldP in terms of the . when H is supposed to be constant dl de . r dk\f df = f ~ THJJ. ^dk + H de . ( \ /? r \ T. We so that have I= kff. i al\ (40). x } iu 11 1> >?> T /f .n 1H + m 11 dl~ 2H df 3 11 ~k He dk de ~ i I df dk ~df dl* if ynn lc yn n I? Now the the coefficient of magnetization depends upon strains. ~n mn m = i d dl m i dl\ 1 ynnkl df) > 11 I mn . changes which take place in the intensity of magnetization when the bar is stretched rather than in terms of dk\dc and dk\df. ! x )1 ') Now by equation (32) d So that these equations become de __ m 3111in 11 \ ~ dk_ mn yn .dl~ (ff yu n ac al ~ m nd d dl~ ynn de dl" d d indf dl* H45). the intensity of magnetization of the bar when under will the action of a strain.
Helmholtz and Kirchhoff was rather different from that of Maxwell. The object of the investigations of v. Ann. the bodies in the electric or magnetic is field must be strained as as that given if they were acted upon by a have certain distribution of stress which in the simplest case the same by Maxwell. The expressions for the strains in a magnetizable substance placed in the magnetic field have also been investigated by v. The effect of stress along the lines of force on the magnetization of iron has been investigated by Villari (Pog?. Maxwell's object was to show that his distribution of stress would produce the same forces between magnetized bodies as those which are observed in the magnetic field. . xxv. 601) has investigated the effect of this on a small soft iron sphere placed in a uniform magnetic field and has shown that it would produce an elongation of the sphere along the lines of force and a contraction at right angles to them.Kirchhoff (Wied. Ann. Helmholtz and Kirchhoff' s object was to show that it follows from the prin ciple of the Conservation of Energy that. We stresses. 385). p. p. while v. Helmholtz (Wied. xxiv. p. the strains intensity produced by these depending upon the alteration of the of magnetization with stress along and perpen in addition to the strain dicular to the lines of force. xui. 52. whatever theory of electricity and magnetism we assume. We may therefore assume that in general this distribution of stress lines of force causes an expansion of the magnet in the direction of the and a contraction in all directions perpendicular to this.
de . except when the magnetizing force is between the critical values. stress at right angles to the lines of at right angles to the lines of force diminishes so that for small values of the magnetizing force extension the magnetization. is Now so that dllde positive is or magnetizing force less or greater negative according as the than the critical value. have opposite signs.a dl z . de and df . Swing's measurements show that than unity. de Hdkldl is always dl anCi dF have the same sign. since Prof. magnetic but when the magnetizing force is greater than this value the extension will diminish as the force increases. we less see by equation dllde and dlldf have opposite signs. Thus. hence (48) that except in this case.the intensity of magnetization Sir is diminished by stretching. As we mentioned before the strain produced by Maxwell's . while for larger values of this force it increases is it. investigated William Thomson also the effect of magnetic force on the intensity of magnetization and found that this was in general opposite to that of tension along the lines of force. when value the extension the the magnetizing force is less than the critical we are investigating will increase with force. dl ano. The critical value of the force in this case however higher than that for tension along the lines of force.
Roy. and that when alter with strains are more powerful than stress. Swing's experiments effect of strain on magnetization (" Experimental Researches in Magnetism. 76. Soc. 225. is i 7 67r E ' where E is one of the constants of elasticity for soft iron .less than the critical value this strain and the strain we have is just investigated act in the same way.H. 30. p. p. XL. placed in a uniform magnetic field where the force at an infinite distance from the sphere is . 585) would seem to show that this must be the case. For 6n the Kirchhoff (Wiedemann's Annalen." Phil. 1847) prove that the length of an iron bar increases when it and as far as the experiments went the is magnetized increase in the length was proportional to the square of the Mr Shelford Bidwell (Proc. those arising from Maxwell's distribution of Prof. 60 1) has shown that the greatest increase in length which Maxwell's stresses can produce in a soft iron sphere whose radius is J?. magnet shortens Comparing these experimental results with our theoretical conclusions we see that they are in accordance is when the the magnetizing force is large they indicate that the strains due to the same cause as that which causes the intensity of magnetization to magnetizing force small. when the force Joule's investigations (Phil Mag. but greater they act in opposite directions. p. xxv. magnetizing force. pp. part n. 1885. Trans. 109) however has lately shown that the when the as magthe netizing force is very large magnetizing force increases.
The diameter nearly ... nl so that 2'4 x io e 8 ' by equation (48) be the elongation due. to the magnetization de ii ... .G. with (49) we see that the part of dej^I due are now considering is very much greater than that due to Maxwell's distribution of stress.Now according to Prof. units. so that if q be Young's modulus load for the wire and 8e the extension produced by the qc = for 2 x io 8 : wrought iron q\n is about 7zS<? 25. so that 7 8 X IO = and therefore by (49) i di = de if i . less. and critical doubtless verv much so that .... so that in this case 8/i = .. (50). of the wire was such that the load..S..... Ewing's experiments the intensity of magnetization of a soft iron wire which was represented by 181 when there was no load was increased to 237 when the wire was loaded with a kilogramme. The value 2 Comparing this to the cause we of dlfde near the is probably exceptionally large in value it is this case.0" per square centimetre in C. of a kilogramme corresponded to a stress of about 2 x 1.
in conjunction the theoretical results t w we have been investigating in t paragraph.me oiner we buuuiu eApeui uie cuuutu vuiue ui L magnetizing force to be approximately the same as t value of the force when the extension is a minimum . 3 Bidwell's discovery that defdl is negative when magnetization exceeds a certain value. There seems however to be reas is fi think that the critical value when the magnet from strain has been very Prof. much underestimated." By the positive effect of stress Prof. Ewing mea stress. If the dilatation in volume e+ zf be denoted by 36. it however much to less. then the part of 8 due to the same cause as that whi makes the intensity of magnetization depend upon strain by (48) given by the equation _^ ~ _ i dl* yn i_ fdj_ it kl \de + 2 dl\f _rrdk_ M df) V ~dl Joule's experiments show that the dilatation in volume if it exists at all must be very small compared fliA *lrmnoftr*n oo TIP* nm c nr^f n Klo. Inde " if at.) expresses his opinion that very small stresses it is doubtful whetl any reversal of the positive effect of stress would reached even at the highest obtainable value of the magnc Ewing (loc. deal only with zation. shows that when the magnetization reaches t value the positive effects of stress must be reversed. T magnet in this case however is not free from stresses as il acted on by those called into play by the magnetization. t an increase of magnetization with an increase of magnetizing force remaining constant. fr\ rlof^r*f if f IT/MI rrli t w .
. value of the intensity of magnetization.. (54). Phil. " (53) 37.. except in the neighbourhood of the critical magnetic forces when dlldc and dlldf are both small. Part n. . .. * " .. .dl de + dl 2 ctf must be small. traction along and perpendicular to the lines of force is produced opposite results. we assume that Joule's experiments prove no change in volume then by equation (52) If that there dl and equation (48) reduces de i dl to dl dk* .. ... will. the results of Sir William Thomson's experiments on the effects of traction along and perpendicular to the lines of ." Part I. the intensity when the magnetization is neither increased nor decreased by a small strain. i.. since by (32) and (47) critical The dk\ dl d e d d .e.. be given by the equation Some Applications of Dynamics to Physical In my paper on Phenomena. so that dllde and dl\df must have opposite This agrees with signs except when they are very small.. Trans. .. force on the intensity of magnetization as.. 1885 this equation has the carried down from equation (51) in the same which was wrong sign.
A be expanded in first. the coefficients of elasticity will do the same. observed. We conclude therefore that the elasticity of an iron bar must be altered by magnetization.itAjde powers of must be a function of so that if e it must contain powers about <?. The coefficients of elasticity however are linear functions of the coefficient of e latter quantity 3 in the Lagrangian function so that if this depends upon the state of magnetization. This effect does not seem to have been If in the expression for A we neglect powers above the second we have ~fl de ' and therefore d d de d'P The e passes right hand side of this equation changes sign when through the value Now the effects of strain on the intensity of magnetization strain and of magnetization upon depend by (32) and (47) . . s the term ye' exists. the coefficient of e in the Lagrangian function will contain the term \yl" and so Avill involve the state of magnetization of the body. . the We may therefore write A = a + fie + y/ + Now if 3 S<? + .
sion the effect of expan and contraction upon the intensity of magnetization and viceversa. the terms in the Lagrangian function depending upon strain and magnetization are a similar method to that employed in the case of we can prove that the twist c due to the same By dilatations cause as that which makes the intensity of magnetization alter with the torsion is given by the equation dr~n Now when d is a twisted bar magnetized is it untwists to a certain extent if the magnetization intense. using the about its axis. experiments as he found that when the stretched beyond a certain limit they soft iron wires were became shorter instead of longer when they were magnetized. We can however in a similar way discuss the effects of torsion wire.me eueci 01 magnetization on me an iron rod to depend upon the strain previously existing in the rod. in such a way that when the strain was less than a critical value magnetization would increase the bu mm we buuuiu expect strain of length of the rod. upon the magnetic is properties of iron Let us now suppose that twist wire which is the only strain in an iron longitudinally magnetized then. and when it was greater than this value magnetization would have the contrary effect and tend to This agrees with the result of Joule's shorten the rod. So far we have only considered 38. and has a twist c same notation as before. but the twist .
Since the twist diminishes with strong magnetization we see by equation (58) that the coefficient of c'\n must be negative when / is large and hence that the coLet us call this efficient of c* in A must be negative. as in this case the twist in a wire increases when longitudinally magnetized. coefficient y. but the apparent coefficient of rigidity is twice the coefficient of . the coefficient 3 of f in the Lagrangian function is . Hence and therefore the coefficient of r in the Lagrangian function must contain a term proportional s Now the coefficient of r\n the Lagrangian function to 7 . . otherwise twist by equation (58) an when A must contain a term in c~ it was magnetized. iy'/ .This shows that if A be expanded in powers of c the power must be untwisted bar would first absent. is proportional to the coefficient of rigidity and hence we see that the rigidity of iron wire will be altered by magnetization.l. so that the same couple will not twist Thus the wire as is much when it is strongly magnetized as when it unmagnetized.r in the Lagrangian function so that in this case the apparent coefficient of rigidity is ' n ' J in this case the effect of strong magnetization is to increase the rigidity. When the will intensity of magnetization is small the opposite be the it is case.
p. also quoted in Prof. If a bar under the influence of a longitudinal magnetizing force is twisted the magnetization increases with small twists but decreases with large ones. The reciprocal relations between torsion and magnetiza tion have been experimentally investigated by Wiedemann (Lehre von der Elektricitat. Chrystal's article Encyclopedia Britannica. in." Comparing these statements with the results we have . the twist increases with weak but diminishes with strong magnetization. " If a wire under the influence of a twisting strain is 5. magnetized. 692) and he arranges These are the corresponding results in parallel columns. The following on Magnetism in the is one set of the corresponding statements. We then twisting the wire will diminish the intensity of magnetization. On the other hand when the intensity of magnetization is so small that magnetizing the wire increases the twist in it then twisting the wire will increase the intensity of magnetization." "V.~f~n T~T 7 nkl dc \ z is very small dP 1 " " dk\ 7~ ) dc) ( v 00 ' / see by this equation that when the magnetization is so strong that magnetizing the wire diminishes the twist in it.d d_ dP we have dc or approximately since d (AP}lndc" dc _ i dl ( ~ ~.
z . when it is on the other side the contrary is true. Let/. f.2eg~ 2/). The existence of a critical twist as well as a critical magnetization makes the verbal enunciation of the relations between torsion and magnetization cumbrous.. y. +/ +/ 2  tef. then if the body is isotropic. the influence of twist on magnetization depends upon the part of V V size of the twist. they are all however expressed by equation (60). fixing the is and configuration if the dielectric free from torsion %n (t where e. but the opposite Further since by true if the magnetization is strong.. z respectively. it follows by equation (60) that the influence of magnetization upon twist must depend upon the size of the twist so that 5 is only true when the twist is on one side of a critical value. the terms in the Lagrangian function of unit volume of the dielectric strains which depend upon the coordinates electric are. Strains in a dielectric produced by the 39. r be the electric displacements parallel to the axes ofx. The strains produced in a dielectric by the electric field can be found by a method so similar to that used in the last two paragraphs that we shall consider them here though they have no connexion with the terms in the Lagrangian function which we have been considering. g are the dilatations parallel to the axes of x.(6i) v.is is true if the magnetization is weak.y. electric field.
+ " r >.? ~f~ S = o ] . Now So that if _/) ' ' ' 477 47T je 2 = x 2 + Y.</! ^ir i  (62).us vaiue mese equations oecome spectively * 2 re h q* + r2 } ~~ H. The term (Xp f Yq + Zr) which occurs in the Lagrangian function can be shown to involve the same .. The Is expansion in volume e+f + g given by the equation *+/+"=o STT Just as in the . )h./ (e +/+ ) + (.. \df dg)} with symmetrical expressions for g and h.v .+ z\ we get from equations (62) n dK  de (dK + (mti) ' (. ^ analogous case of magnetism these are not the only strains produced in the dielectric by the electric field.2 + f. dK\\ . R 3 i (dK n^ae \ $m dK dK\ r +jf + r t df dg ) (64).
viz. though most dielectrics expand when placed the contrary contract.exist in the electric field. 1880) and others show of Quincke (Phil. Mag. will be of the The effect of this distribution of all stress its nature same character for depends more upon the field than dielectrics. in the same electric field very example. shows that i/AT must contain a term in 2 specific inductive capacity depend upon strain. p. a tension JZR^lBir along the lines of force and a pressure of the same intensity at right angles to them. and distribution of force throughout the electric dielectric. that the behaviour of different is dielectrics different. x. the fatty oils on This difference of behaviour shows any rate. as if it only contained the second powers placing the dielectric the in an electric field would merely be equivalent to changing the coefficients of elasticity of the body and so could not . electric field is due to the same cause as that which makes it. the expression for ijK when expanded in powers of e must contain the first power of the strains as well as the second. upon the nature of the The experiments when placed Thus. Quincke has shown that duced in this the coefficients of elasticity of a electric when an <? displacement is pro when expanded in powers of e and is another proof that the specific inductive capacity depends upon the strain in Since part of the strain of a dielectric in an the dielectric. the strains due to the same cause as that which makes the specific inductive capacity depend upon the strain are greater than those produced by Maxwell's distribution of dielectric are altered stress. for in 30. that in many cases at an electric field.
to i part in 400 for each degree centigrade of temperature. ing in the case of glass. amount. for which it is largest. then magnetism must behave as if it possessed the inertia. greater than those in the corresponding The dependence of upon strain is K probably much less than that of k. Thus there is a com paratively small difference capacities between the specific inductive of various substances. In soft iron and steel the conditions are made so com . No experiments seem to have been made on the effect of torsion on electrification or of electrification 40.do this are much case in magnetism. motion of the molecules of the magnet. mica and glass is small. as it does according to all molecular theories of magnetism. the coefficient of magnetic induction. while some recent experiments made by Mr Cassie in the Cavendish Laboratory have shown that the induction effect capacities of changes of temperature on the specific inductive of ebonite. Again. Influence of inertia on magnetic pheno In the preceding investigations we have supposed magnetic changes to take place so slowly that the If however a change in effects of inertia may be neglected. the magnetization involves. while the coefficient of magnetic induction of iron is enormously greater than that of any other substance. For the specific inductive capacity seems to be much more independent of the molecular state is of the dielectric than the coefficient of magnetic induction of the molecular state of soft iron'. mena. the coefficient of magnetic is known to be much affected by changes in temperature. upon torsion.
cations. and those depending solely on the magnetic coordinates. for when / 2 passed through the value ijkM the crystal would swing through a right angle. n it exists. as only would probably be detected one of these. If #"is periodic and varies as <?#' then by (65) r_ kH kMp > s so that if/ be so large that i. The would be to introduce into the equations of magnetization a term where / is the intensity of magnetization. quartz. the crystal if para magnetic for a steady' magnetic force a variable one and vice versa. Ine ettect. let us consider those terms in the expression for the kinetic The term (y) We have considered jj> in the Lagrangian func the terms now . p. has ever been suspected of showing residual effect of inertia mag netism (see Tumlirz. xxvir. 41. Wied. tion. 133. depending upon the squares of the velocities of the electrical coordinates. most easily in the case of crystals. The equations of magnetization would therefore be of the form where Jfis the external magnetic force. 1886). Ann. will be diamagnetic for Changes of this kind could be detected very readily if the crystal were freely suspended in the magnetic field.
dp dz  V /. C parallel to the axes of x. y. So that these terms are of the form Considering the Lagrangian Equation for the electrical coordinate. z.flows through the element of dx'dy'dz' is magnetized to the is volume dxdydz and the volume intensities A. /A.. then the kinetic energy L possessed by the system ay ) dxdydzdx'dy'dz'.. we see that there is an electromotive force . C=v. jB = rf. v respectively. fr dz \ dx dy J ) .\ dp (v . Now we represent the intensity of magnetization by is the momentum corresponding to a kinosthenic t\% where or speed coordinate and 77 is a vector quantity. B. dp\ +V ( dp . z respectively. Let us denote these components by X. y. Since T? is a vector quantity it may be resolved into com ponents parallel to the axes of x. then we may put A Making T = \. w dy .r dx . this substitution we have L=\ f 21 / ( L V /A f.(t>*i\ where p is the reciprocal of the distance between the elements dxdydz and dx'dy'dz'.
* dp' B /. The magnetic force parallel to x acting on the element is dx'dy'dz by 33 equal to idL d\ so that the magnetic force parallel to is x per unit volume equal to . * with similar expressions for the magnetic forces parallel to These expressions agree with those the axes of y and z. .J or f .with corresponding expressions for the electromotive forcesaxes of y and z. Again there is a mechanical force acting on the element dxdydz whose component parallel to the axis of x is dL ' dx If we call fj 'j >j &x dy dz / or ( T? [B ^ dp  n dp\ C^.dp I A 4. given by Ampere for the magnetic force produced by a system of currents. parallel to the forces These are the usual expressions for the electromotive due to the variations of the magnetic field.
quantities Electricity 69 denoted by the same symbols is in Maxwell's and Magnetism. In the above investigation we have assumed that we the element without altering the current . Since it du dv dw + . . ^+v^+wf} dxdydz dx dz J dy if all o the circuits are closed. Since the force on the element dxdydz dL dx' we see that the force on unit volume may be written U or dF dx +V dG . if we suppose the current to move with the elements we shall get could move Maxwell's expression exactly. So that as long as the circuits is are closed the effect of the translator}' forces if the same as they were given by Maxwell's expressions.. ay dz . dx \W dH  dx .. v \'j (dG This dF\ ~j~ {dx \~ ay) (dF .dm w }~j j~ \dz dx ( +u dF J r+vr dx dy ' dF + =.MECHANICAL FORCE DUE TO A CURRENT.= o 7..+ dx dy dz follows that dF dF dF\. dz differs from Maxwell's expression U for the same force by the term dF = ax +V dF 3 +W dF =.
when a current flows along a longi p... the mechanical force on a current in a magnetic field and the mechanical force on a magnet placed near a current.. in.... wire. the production of a magnetic field L by a current..with corresponding expressions for the forces parallel to y and s.. 17! the intensity I./(f) being some function of principle to this term we see that Applying Hamilton's indicates the existence it of a couple tending to twist the wire equal to (75).. 689) has that tudinally magnetized wire. Wiedemann (Elektricitdt.. (74). We see by this example how from the existence of a we can deduce the laws for single term in the expression of the induction of currents... and c the twist about the axis of the c.. Applying Lagranere's eauation for the .. where y is the of magnetization current flowing along the wire. magnetized iron wire produced G... it produces a couple tending to This shows that there must be a term in the Lagrangian function for the wire of the form fVfrlt . Twist in a by a current.... 42. shown Prof..... twist the wire. Thus the force on the magnet is equal and opposite to that on the current.
and any alteration in the longitudinal magnetization of a twisted iron wire must produce one lasting as long as the magnetization changes. since any term in the Lagrangiatt function indicates an effect similar to that which would be produced by an external magnetic force equal to \dL . The production of an electromotive force by twisting a longitudinally magnetized iron wire mentally verified. and in this case there is no alteration in the number of lines of force passing through the circuit. has been experi Again. if we consider Lagrange's equations for the coordinates fixing the magnetic configuration.dt dy ' the existence of this term shows that there is an electro motive force along the wire equal to 'hat is  Thus twisting a longitudinally magnetized iron wire must produce an electromotive force which lasts as long as the twist is changing. Hence Faraday's rule that the electromotive force round the circuit due to induction equals the rate of diminution in the number of lines of not apply to the case of a twisted iron wire. for we might get an electromotive force round a circuit made of such a wire by moving it in the plane of force passing through it. will the magnetic force.
y. for as we shall see directly this phenomenon x. indicates the existence in the Lagrangian function of terms of this kind. 43. connexion with Hall's phe nomenon. a. served by Prof. y are the components of the magnetic force and f. and its components parallel to the axes of x. Mag. and that this electromotive force at any point is parallel and proportional to the field mechanical force acting on the conductor conveying the Thus the electromotive force is at current at that point. 301. G. h are the components of the electric displacement if the medium is a .) that currents are flowing through a conductor placed in a magnetic field. involving are also interesting from their and magnetic coordinates. both the electric The terms we are con sidering. 692). p. Hall discovered (Phil. right angles both to the direction of the current and the magnetic induction.tending to magnetize it longitudinally. So that if a current of electricity passes along a twisted wire or if a wire conveying a current of electricity be twisted the wire will be These effects have been oblongitudinally magnetized. Hall's phenomenon. f3. Wiedernann (Elektridtdt. in. 2 are respectively given by the expressions where C' is medium through which a constant depending upon the nature of the the current is flowing. g. there is an electromotive force due to the when even though it remains constant.
the rate of change of the magnetic force and the angle between the electric displacement and the direction in is D H which the change in the magnetic force is greatest If be the original electromotive force then since the P Hall electromotive force is very small we have approximately : ATT .TJLI.W +?(** yf} + h (/?/ o.v*J xu... LJi WVJIV. the resultant electrostatic displacement. Let us consider the Lagrangian equation for the electric It indicates the existence of an electromo tive force parallel to the axis of x equal to _ or in this case ddL dL "dtjf^df C'(&yg) + %C'(ygph} .. I ) W (Ays.i.... This latter force is at right angles both to the direction of electric displacement and to that in which the change in the magnetic force is greatest .(. is \C'HD where sin 0.g}} ... \ /*. of these terms corresponds to the Hall effect. Wg <VA.*.. JL tK* w^wj o_ eta u JA.(78) expression for the volume of the medium... in the Lagrangian function of unit displacement/. the second to. L/.an electromotive force tending to displace the lines of electrostatic force..y ttijiva. the magnitude of the force . Os 1881) have shown that the existence of this force proves that there is a term equal to j. The first (79). J.
p. HalFs experiments show that C' in electromagnetic 5 21 is of the order io~ measure is at most of order io~ and . If r. x. z respectively. /3. easiest of magnetic instead of electromotive force.) Let us now consider Hall's effect from the point of view Perhaps the be to suppose that the magnetic forces are produced by an element of volume dx'dy'dz' C parallel to the axes of magnetized to intensities A. 304. for a point outside the magnet \ dxr and dy r dz r) h dx ' dy a. detection by experiment. see too from the expression for this force that it absolutely vanishes when both the electric displacement and the magnetic force are stationary. x. Mag. Now K so that the ratio of the disturbing force to the original force is of the order io~ 37 H sin 6. and these were the conditions We when Hall tried unsuccessfully to detect the existence of his effect in an insulator (Phil. and is thus much too small for there to be any chance of its. O is the magnetic potential of this element at a distance then. y. 1880. y dz' Substituting these values for y in the expression (78) . way to do this will .CKJfsm O7T 6.
. i or A a I . ' l j b dydzr ~/S\ y<:>J dx'dy'dz'. the magnetic force axis of on the element dx'dy'dz i parallel to the x will be dL t <&' so that in this case the magnetic force parallel to x per unit volume is or if ^} + {V V  i+ {*^} . .. li i.+ .. g.. .. . h through unit volume at the point (xyz) is similarly the magnetic forces parallel to y and z are (84)..+{hfhf\ fgfg] ^ d^/y r V/j r {iy<b . \ {/. y'... (8x) then the magnetic force at the points ic'. /.. z parallel to the axis of x due to the electric displacements f..p/4 3 .1..
... Let us suppose that we have a small sphere whose centre is at the point where we require the magnetic force.. magnetized to the intensities A... where dfy <Nf dz' it/' V = $H$dxdydz . If the point at is volume throughout inside the which we wish to find the magnetic force volume occupied by the electric displacements we must modify the preceding results... J?. y. (85).as that which produces Hall's effect are d^ <&' respectively... C z respectively.. the integration being extended over the which there are electric displacements. parallel to the axes of x.. o hence the components of the magnetic force due to the electric displacement at the point where the force is measured are So that the general expression for the components of the magnetic force due to the cause producing the Hall effect .. Then inside the sphere So that the Lagrangian function dxdydz inside the sphere is  for an element of volume C^{A (ghgk) +JB(hfhf) + C(fgfg)\dxdydz.....
. g. .. h. these forces will be very small.. (86).. is a very small quantity.. and v the Substituting these values we see hfkf=Q .. h vary very rapidly that we could expect to electric have any chance of detecting them.. as are also f......+ f. (88)......... where /. and it only when f. w is the amplitude of the oscillation. We shall therefore calculate the magnitude of these forces when the displacement changes with the greatest rapidity we can produce in an experiment.. g. A the wave length velocity of propagation of light. Let us suppose that we have a circularly polarized ray travelling along the axis of z and that the electric displace ments are given by the equations f= w cos A 27r (vt I z) \ g=wsmr(vfz) A where * . ment at the point h are the components of the electric displacewhere the magnetic force is measured and Since C' is ^ is given by equation (81).. This if the Electromagnetic Theory of Light is true will be when the electric displacements are those which accompany the propagation of light..(87). g..rC'(A/V)[ .
7 or 3 x I0? Assuming the wave length to be 6 x io~ 8 . a little to be io~ we see line and greater than that of the that the magnetic force produced by circularly polarized light as intense as strong sunlight cannot be greater than 2 D C x io~ 18 . is w given as 6 x io 7 in electromagnetic measure. . The maximum electromotive force in this case ii. 793. Vol. which is much The direction too small to be detected by experiments. direction of the magnetic force is related to the of rotation of the electric displacement in a circularly polarized 'ray like translation and rotation in a lefthanded screw.and thus by equation propagated equal to (36) the circularly polarized ray it is in the direction along which produces a magnetic force 27TZ' we can deduce the value of for strong sunlight from the data given in Maxwell's Electricity and Magnetism. of the displacement corresponding to this is K. 6 47T x i o . which is 5 . the maximum value w.
which . of an external magnetic force we in the case we have just investigated.. .ularly polarized light In this case by the rotate the plane of produces a magnetic force parallel it is the direction in which travelling. a beam of arization .s of magnetic force are more or less parallel to the 2ction of propagation of the light. y be looked upon as the converse of this.
we shall accordingly Let us consider the mutual by the coordinates p two quantities fixed and q upon each other. RECIPROCAL RELATIONS BETWEEN PHYSICAL FORCES WHEN THE SYSTEMS EXERTING THEM ARE IN A STEADY STATE.CHAPTER ' V. then P P p p acting upon the in a definite way the and the amount of the suffers a alteration q. Let us effect of of type suppose that we have a force will alter the coordinate system. When however the system is in a steady state the reciprocal relations between the various physical forces become so simple that they seem deserving of special treatment. P must Then q and that SP is the amount by be increased in order to keep p the same as since the system is in a steady state if L be the Lagrangian function we have dL ~ . and consider them separately. may depend upon value of the other coordinate Let us suppose that q small alteration which before. preceding methods are applicable to systems whether steady or variable. 44. THE in all states.
169 and forms one of those reciprocal relations which exist in in Physical Science. Thus if depends upon q then Q will depend upon p and vice versa.l\ ow it we nave a lorce y 01 type q producing a detinue change in the coordinate q then if we alter in order to keep q constant alter Q p by Sp we must by some quantity 8<2. in the Theory of Sound. and since Q ^ and ^ dq Q ^ + BQ^M^fZy f dpdq dq ^ we have so that by (89) and (90) 8Q = d*L rjp (90) we have 'dP\ J$ = (?Q\ constant ( T\ \&p is / q constant Or the alteration in is P when q increased by unity. q being constant. Vol. And P we of of notice that if by increasing q we increase the "spring" p q. Chapter 5. p being is constant. . then by increasing p we shall increase the " " spring " Equation (91) is analogous to the thermodynamical relations" given in Maxwell's Theory of Heat^. physics and which so often enable us to duplicate discoveries The consequences of reciprocal relations of a different kind are considered by Lord Rayleigh i. the same as the alteration in Q when p increased by unity.
magnetic force and /the P \ le constant Ji\ =( \ //constant (1C d . Let be the electro E motive force. and T its surface tension. then in this case for the effect of pressure p we have . then the increase in Q required to keep its point of application at rest when / is increased by unity..action of any number of forces two of which are jPand Q. x ( solution Again when a current passes through an electrolyte in it decomposes it and the strength of the solution and changes. in general will. //"the being the tension. will also be the amount by which point of application P must be increased to prevent moving when q is increased by unity. relation. we see by this equation that if the force required to produce a given extension in an iron wire is altered by magnetizing the wire then the magnetic force required to magnetize the wire to a given intensity will be altered by straining the wire : and that these alterations will be connected by the following intensity of magnetization. S its surface. y the current. and in this case equation (91) shows that the electromotive force required to send a given current through a cell containing the solution will be altered by pressure and by any change in the free surface of the solution. the volume and the surface tension of the solution. v the volume of the solution. this change in the strength of the solution may.. e the extension of the wire. its Or again. change the coefficient of compressibility.
we shall suppose that none of this is redissolved. The data for calculating dkjdy in this case are the fol To get an lowing to : of unit quantity of electricity corresponds B the decomposition of about 4/3 x io~ grammes of lithium chloride. the volume of the solution being i cubic centimetre. k is also constant so that and therefore from (93) v\ ) vj dy dk dk dp rfk so that if increase 8 the to the pressure is increased from z 1 in the electromotive force required to keep the is P P current constant given by (94). then the passage of a unit quantity of electricity will The passage withdraw this quantity of salt from the solution. Rontgen's and Schneider's experiments (Wiedemann's . idea of the magnitude of this effect let us take the case of a solution of chloride of lithium.v\dk_ when y is constant.
but that the since coefficient of compressibility is unaltered. show that the effect of pressure on a solution of thissalt would be much' greater than that on the lithium chloride solution. so that if fdj\ k dv . Io18 ^ Z'2 X IO 10 IO 4 that the pressure of 1000 atmospheres would diminish the counter electromotive force by about 1/400 of a volt.proportional to the quantity of salt. Then the passage of the unit of electricity increases the volume by dvjdy we must apply an additional pressure kdv{v dy tokeep the volume constant. then the subtraction of ~3 43 x 10 grammes from i cubic centimetre will diminish the modulus by about 7 i part in 100. . Let us altered now suppose that the volume of the solution is by the passage of an electric current.t o~ 2 approximately. Now k for water is about z'z x io in . hence j = . which 9 we have in absolute measure is about io . so that if E is the change produced by a pressure of 1000 atmospheres. is The numbers given by Rontgen and Schneider effect of for the carbonate of soda on the coefficient of compres sibility.
In order to see of what order this effect is likely to be. Let us suppose we are electrolysing water. and since the specific gravity of the salt is 2 6. we see from this equation that is given W = ty$L When are so (95) the electric current goes through a salt solution the changes which take place and which alter the volume numerous that it is existing data the change which takes place not possible to calculate from in the volume when unit quantity of electricity passes through the solution. 9 x io~" grammes of water are electrolysed. When unit quantity of electricity goes through a solution of sulphate of potassium 3 it electrolyses about 9 x io~ grammes of salt. let us is suppose that the change in the volume comparable with the volume of the salt electrolysed. We will now consider the case when gas is given off. If unit quantity of electricity goes through the water. enclosed by a cylinder with a mdveable piston. the volume of 4 the water therefore diminishes bv qxio" cubic centi .so that since kdvjvQ the change in the counter electromotive force by the equation E dp.  volume of this the is about hence in this case we may suppose and that comparable with 35 is x io~ 3 that dvfdy is change in the counter electromotive force produced by 1000 atmospheres of the order 3 5 x % 10<i > or about 1/28 of a volt. above which we have air. the 3'5 x io~ 3 .
l so that If the pressure S is increased from P i to P s the change in E is given by the equation 165 x io x log 6 S= force is ^ .volume itiiJciiiJuig vuuDiani. in pressure due to the disappearance of if v be the volume of the gas above the water Q x io~. The diminution the water is. vviic. CICV^LII^IL^ Uciaacs. For a thousand atmospheres the counter electromotive increased by .ii uuii UJ.9 x io' ^i 4 x (P2 . V and the increase due to the oxygen is one half of this. v 4 the increase in pressure due to the io~ gen is if the temperature is o C. hence dyj v so that by (95) v = dv But v x IO {1*65 l G  x* o px y io~ 4 .PJ. 10 I'lXIO X grammes of hydro I0 ~" .
show that the addition of 6 parts by weight of lithium chloride to 100 of water increases the surface tension by about 3 parts in 100. xxix. The passage of i unit of electricity decomposes 3 about 4 '3 x io~ grammes of lithium chloride. so that if v be the volume of the solution i ~rrt dT T~ i . The effect of surface tension is given by fdE\ jri I \O / y constant I _(dT\ ~3 \ I \ uy / s constant This effect will in general be very small. 1886)._ T V * dy v io 3 ^L^ o 2 V " io > 2  6 V A "1 V A A ^ < X Trt""" U JL =and for 2 x 3 io~ . water T= 81.approximately. for example in the case of chloride of lithium. p.so that the counter electromotive force is increased by about oneeighth of a volt. 209. dT _ dy 162 x io~ l> 2 so that ' and therefore by (96) dE = ~dS or if the 16*2 x ro~ 2 ' v volume remains constant the effect of increasing the surface by S is to diminish the counter electromotive . the experiments of Rontgen and Schneider (Wiedemann's Annalen.
preceding investigation is on the supposition that the electrolyte is in contact with the air.and 2 162 x io~ If/ were of the order of molecular distances say io~ 7 then 8J2 = i6'2 x to is 5 . to decompose an electrolyte in a porous plate it would be larger than that required to decompose when it is Again. so that the electromotive force required to decompose an electrolyte which absorbs a gas produced by the passage electrolyte of the current will be different when the falls required when the interstices of a porous plate from that it is in an ordinary electrolytic cell. The so that the electromotive force required in bulk. or the counter electromotive force diminished by about = 'oi 6 volts. if it were in contact with a solid such as glass the withdrawal of the electrolyte from the solution on the passage of the current would increase the surface tension between the liquid and the solid. the surface tension of liquids is altered when they absorb gases. .
CHAPTER VI. ' in unit volume NO is the energy of translatory motion of the molecules at the tempe There seems good reason for believing that NO is a part of the kinetic energy of the molecules when these are . magnetism and elasticity and have not discussed any phenomenon in which We shall now go on however to temperature effects occur. and there the temperature is the mean energy due to the translatory be the motion of the molecules of the gas. So that if N number of molecules of the gas rature 9. endeavour to extend the methods we have hitherto used to those cases in which we have to consider the effects of temperature upon the properties of bodies. The only case in which a dynamical conception of temperature has been attained is in the Kinetic Theory of Gases. WE have only considered so far the relations between the phenomena in electricity. EFFECT OF TEMPERATURE UPON THE PROPERTIES OF BODIES. Before doing this however we must endeavour to arrive at some dynamical interpretation of temperature. 45.
reader should refer on this point to Maxwell's Theory of Another reason for supposing that the Heat. . in which supposition is made.same time led heat is to the conclusion that the energy of sensible energy due to the motion of the molecules and is The therefore part of the kinetic energy of the system. that is is. p. temperature in the liquid as well as in the gaseous condition is measured by the mean energy of translation of the molecules is. where the rise in proportional to the energy communicated to the system. and that this theory agrees well with the facts in many important respects. that This following illustration will show that it is probable when we have two bodies in contact the collisionswill between the molecules solids tend to equalize the mean energy of this translatory motion when these bodies are and liquids as well as when they are gases. that Van der Waals (Die Continuitdt des gasformigen und jliissigen Zusfandes} has given a theory of the molecular constitution of bodies in those states which between the liquid and gaseous. 301. so that in this important respect the translatory energy has the same property as tempe rature. And again since most solids and liquids are capable of getting into a are intermediate this state where their specific heat is constant. Let us suppose that we have two different substances. The mean translatory energies of two substances in contact thus mean tend to become equal. we are led to suppose that the kinetic energy of some particular kind is a linear function of the temperature temperature.
the molecule. w and after impact. v the velocity of and a the angle its direction of motion makes with the normal to the plane before impact. or what amounts to the the molecules on the surface of the Let us suppose that the action between the molecule and the plane is the same as that between a perfectly elastic sphere and plane. . .(M.m} vw cos a}.from moving through more than a distance comparable with molecular distances. Since the mass of the plane is very only much greater than that move through a small of a molecule and since it can the distance in one direction velocity of the plane will be very small compared with that of the molecules we shall suppose that it is so small that the number of molecules which are than the plane may be same thing that all substances which are moving towards the plane strike it. and that none of those which are moving away from the plane do so. V the velocity its velocity the mass of the plane. (M+mf AMiri*1 vw cos a}. moving more slowly neglected. Then we may easily show ' that . . Let m be the mass of an A molecule. M W before and after it is struck by the molecule.mv s cos 3 a . (97). rj 8 z/ } 2 {Mw* . we sum of have rj=.m{ l V*v*}=z 2 of r^rf. mv 2 cos a(Mm} v ' 3 ' Let us take the effects all the equations representing the the collisions which take place in unit time.
we have 2 (M . and since all its average velocity is zero. we have similarly and we have also . then Since the directions of motion of the equally distributed $mtf cos a 2 A molecules are = l 2mv = ^V^. the number of such molecules and TV"/ the number of collisions.in) vw cos a = o.change in Q l in unit time If N' be the number of collisions and the mean kinetic energy of the plane. m' N B l the mass of a molecule. 2 Since the plane is supposed to move so slowly that the molecules moving towards it strike it. so that equation (97) becomes If Os be the average translatory kinetic energy of the molecules which strike the plane in unit time.
and we should expect it would hold eauallv well for . and it will do so if we give it the mean kinetic energy of the If this is plane does not alter in unit time. vanishes and we have by (100) the case 80 so that a+b if m'NJ (M+ mj mN' (M+inf ' ' Substituting these values for 2^^/3. remain equal these thus the exactly mean respects 2 they will translatory energy behaves in like temperature. if Os is greater than 6 V versa. and equations (98) and (99). 1 will increase is and 6.and not such an initial velocity that as a storer of energy. There seems and if &l equal to nothing in the above illustration to restrict it to the case of gases. we have 2 Mai) ff . will and vice . 20$ 2 /3 in 3 (a + l 2 b) Thus diminish.
We have these to latter coordinates entirely under our control finite and subject strength limitations imposed by the of dielectrics. but we have no control over the coordinates individually. We may therefore call these coordinates "uncon property is that we can not oblige any individual coordinate to take any value which may be assigned. of materials. If the term . . Their fundamental of dealing with individual molecules. Let us denote this part of the kinetic energy by where 11 is a coordinate helping to fix the position or con see at once that there is figuration of a molecule. on the other hand. liquid or gas. with the coordinates fixing the separate moving parts of the systems whose kinetic energy constitutes the temperaWe can it is true affect the average ture of the body. value of certain functions of a large number of these coordinates. electric fix and magnetic certain configuration the geometrical.solid. Since we have no power strainable" coordinates. quite different. essential difference between these coordinates and those We an we have hitherto been considering and which strain. the "controllable" coordinates must merely fix the position of a large number of molecules as a whole. the strength and magnetic saturation please. of the system. is proportional to the temperature. trollable we may make them fitly We may therefore It is take any value we call these coordinates con coordinates.
T c corresponds to what v. otherwise the energy of the system would be altered by reversing the motion of all the "unconstrainable" coordinates." There will not be any terms in the kinetic energy involving the product of the velocities of an "unconstrainable" and a "controllable" coordinate. otherwise the where the coefficients (uu)' do not involve phenomenon would be influenced more by the motion of <jf> some shall particular molecule than by that of others.. one depending on the motion of "unconstrainable" coordinates. We assume that the temperature. n..}. p. We may conveniently divide the kinetic energy of a system into two parts.} (102). absolute temperature this is proportional to the the other depending on the motion of the "controllable" coordinates. 6.)'+.... then if <I> be the external . Helmholtz in ( paper on "Die Thermodynamik chemischer Vorgdnge" Wissenschaftliche Abhandlungen. and we shall assume that 6. 47.} : (101). 958) calls "die freie Energie. where Cdoes not involve any of the "controllable" coordinates which fix the configuration of the system. Let us suppose that < is a controllable coordinate which enters into the expression for that part of the kinetic energy which expresses the temperature. is proportional to &{()* that is +.. we shall denote by his T c. which we shall denote by Tu . 8 that = C{(?0 + .
. and therefore by (104) &_=*** T*dT v . ........ .. . #^~2* Tn is ^ )f </* <fy Now by equation (103) of the form i/fo) where (tat)' {()'*+}' </>..so that *= ddT dT _dJ\..... d$ us suppose that energy is communicated to 48.... and partly through of work commustrainable" coordinates: let the quantity If the motion of the nicated in the latter way be SQ. . dV t c . differentiating this equation controllable variable is on the supposition that all the coordinates are constant and that the only on the motion of "unconthe energy depending we have trollable" coordinates..... + ......... does not involve so that we have and therefore *= ^fr. (105). partly by the action of the external the "uncon"controllable" coordinates. ^ l (106). Now let forces on the the system.
.. we get Since the change in the configuration is that which actually takes place in the time 8^ we have 8/=S0.. e Now and since 8r = e + s80 l9 c 80 d<j) ..energy corresponding to temperature. SQ may be regarded as a quantity of heat communicated to the system... (109).. if <f> Denotes a "controllable" coordinate.. We have by the Conservation of Energy.. ^ff*} +8 be completely fixed by the controllable Now.. V . (107)....... T c is " controllable " a quadratic function of the velocities of the coordinates.. so that and therefore equation (107) s becomes e= ss if. ) (108). 8T + BTu +SV ....... we have and therefore +# so that by subtracting (108) from (109) .....
J fy constant to the Let us suppose that the quantity of work communicated system is just sufficient to prevent u from changing. T then or .J   temperature Remembering that J^ is proportional to the absolute $.98 So that DYNAMICS. /Tn constant I ~. SQ dT dT ^ *\jtjfitt (J c s + dV ^~ we have Substituting for <E> the value given by (103) but by (106) <Wn = _ d$ so that T (^\ \dT. we see that equation (115) becomes \ d$ / e constant \ dQ ) A constant ..
_ t f (<j>) ^ we see by (113) that or ^?=281og/tt)+81og7. 209) and Jahn (Wied: Ann. 21. Law it of Thermodynamics.Ul J. The amount which can be . The conclusions at which he arrives have been verified by the experiments of Czapsld (Wied. UciniUUy Urt. is if all the work done on the system is done by means of forces of the types of the various controllable coordinates.ui the variation of the electromotive force of galvanic cells with temperature. p.UUtjS clliu a^jmco IL L<J uio v^cioi. If S(2 21. Since dT. so that SQ Tu is a perfect differential. that  /(/> constant \ "<P /(? constant 49. 491). pp. n * (118). Ann. shews that is analogous to the Second and we see by the analogy that energy arising from the motion of quantities This fixed by "unconstrainable" coordinates can only be partly converted into work spent in moving the quantities fixed by the " controllable" coordinates. 28. then we have by equation (114) = o.
and instead of (114) Since S& and (116) still holds.S Ffo constant))/^. $TU vanish together we see that equation Equations (117) and (118) however require We have now (SQ ."controllable coordinates. To include this case we must suppose V is a function of its the temperature as well as of the <'s. we have . We equation (116) to determine the effects due to the variation of various physical quantities with temperature. remained is unchanged. and that value in the neighbourhood of the temperature corresponding to a change of state in the substance varies very rapidly. type In equation (116) let us suppose that * is a stress of e. differential. In this case we have 6 being the temperature. modification. 50. shall Relations between heat and strain. a perfect 1 instead of &Q/TH . When however the system potential energy may in a portion of a solid or liquid the by some alteration in the state of aggregation be changed without there being any correthe controllable that sponding change coordinates. then using the same notation as in 35. now apply and shall begin by considering the effects the variation of the coefficients of elasticity m produced by and with temperature.
and by (116) 8Q..iiuiu ciieiijiguig vvucij... Papers.. . heat must be supplied to keep the temperature of a bar constant when it is lengthened. r ('/ and thus the coefficients of elasticity diminish as the temperature increases.. uy uc is given uy LUC equation ~ 8(2 =~ if IY/W ^ +/+ ^ + . e is uicicascu. we a couple tending to twist the bar about the axis have. p.. Vol.. (121). 309).. the heat required by unit volume of the bar to keep the temperature from changing therefore is when a increased by Sa is given by the equation SQ = so that it will 6^aSa .. cool increases.. the coefficient of rigidity diminishes as the temperature to itself. = dn a' ~dd . $ d3> ~dB na. as is usually the case. the Second in his The preceding results were first obtained by means of Law of Thermodynamics by Sir William Thomson paper on the Dynamical Theory of Heat (Collected i...' dn .. If $ of x. .. . (IV if a rod which if left is already twisted is twisted still further provided. if a is the twist about that axis. and hence if the bar is left to itself and not supplied with heat it will cool when is it is extended....
we have 'f f constant " uv so that S<2. and that at about. '0004 for mica. 1 K i &K = !t6 ' 2 r % r 1 ' g 1 dK = in . mica and ebonite. have shewn that the specific inductive capacity of these dielectrics. .inductive capacity of the dielectric. r ^ 000 7 for ebonite. the heat which must be supplied to unit volume its of the dielectric in order to prevent temperature changing S/j is when the electric displacement is increased by by (116) given by the equation Some recent experiments made by Mr Cassie in the Caven dish Laboratory on the effect of temperature on the specific inductive capacities of glass. increases as the temperature increases. d: = ~piece of glass to enable ' Thus the heat which must be supplied its to unit volume of a temperature to remain constant when it is electrified is by (123) 27T '002 ==. 30 C.
when parts Sir of the William Thomson in the paper just quoted. Thermal that $ if is Then k be the coefficient of magnetic induction so that \ ) /j constant = I dk ~^Tfi # And unit stant therefore 8Q volume of the magnet the heat which must be supplied to to keep its temperature conis when the intensity of magnetization increased by 87 is by equation (116) given by the equation so that if the coefficient of magnetization decreases as the temperature increases then a magnet is will get heated there when fore its intensity of magnetization it increased.to it from electrical sources. . and moves from weak to strong This was pointed out by magnetic field. effects of Magnetization. We force is see also be cooled when weak to by equation (123) that a piece of glass will it moves from a place where the electric one where it is strong. Let us a magnetic force magnetizing a piece of soft iron or other magnetizable substance to the intensity 52. now suppose I.
indicating the dissipation of a finite quantity of energy proportional to the area of the curve. but also on the phenomenon called so that the previous magnetic history of the substance curve representing the relation between intensity of magneti: zation (ordinate) and magnetic force (abscissa). and this . This causes the intensity of magnetization to depend not only on the strength of the magnetic force. will be of the figure. p. kind shewn in the accompanying and will enclose a finite area. n). as the mag netic force goes through a complete cycle. PhiL Trans. Another thing which would increase the the difficulty is by Ewing hysteresis (Experimental Investigation on Magnetism. 1885.magnetic fields is rendered difficult from the heating effect produced by the electric currents induced in the magnet by the alteration in the number of lines of magnetic force passing through it.
weak to places of strong magnetic force and vice That when the body where the magnetic force critical value. 2. so that a piece of nickel will get warmer when it moves from a weak to a strong part of the magnetic field. That when a magnetizable body moves in a magnetic where the force is everywhere less than the critical value. Taking these results in conjunction with equation (125) we see. The coefficient of temperature if value the coefficient of magnetization diminishes as the temperature increases. The smaller the magnetizing force the greater the influence of temperature upon the coefficient of magnetization.at the following results. weak to places of strong magnetic force and vice The coefficient of magnetization of nickel diminishes as the temperature increases. its placed in a magnetic field everywhere greater than the temperature will rise when it moves from is is places of versa. so that a piece of cobalt will cool as it moves from a weak to a . The coefficient of magnetization of cobalt on the other hand increases as the temperature increases. but when the magnetizing force exceeds this the magnetizing force. its temperature will tend to fall when it moves from field places of versa. 1. The influence of temperature coefficient of magnetization upon the magnitude of the depends upon the magnitude of magnetization increases with the the magnetizing force does not exceed a certain value.
CHAPTER VII. since behaves with regard to heat in the opposite specific heat. result and heat by saying that the specific heat of electricity in copper brass is positive. which inequalities of temperature in a substance give rise to electromotive forces. Sir William Thomson has shewn that when a current of electricity flows along an unequally heated bar it carries with it as it flows from a hot to a cold place either heat or cold if it is : heat if the bar is made of brass or copper. reciprocal relations. ELECTROMOTIVE FORCES DUE TO DIFFERENCES OF TEMPERATURE. that electromotive forces by the consideration of the must be deis veloped in any conductor the temperature of which not . it heat with . cold made of iron. way to a fluid possessing It follows from this result. WE shall now go on to consider various cases in 53. just as if specific it the is " heat" of 'were a real fluid possessing specific electricity in iron on the other electricity in iron hand said to be negative. Sir William Thomson expressed this. since the electricity in this case carries.
..+. the quantities are quantities not explicitly involving of electricity which have passed axes. <$g. s d . taking the whole volume. and equal to the of Sf. h explicitly.. z respectively Let us write for the sake of brevity + r (Vyg) + r. which expresses the part of the kinetic energy of unit. by hypothesis (inf) involves we may write where f(e) denotes some function of e.Let us suppose that in the term {(*) u. d .}. . S/i which this term contributes when is the variation of the Lagrangian function The term we are considering is. By Hamilton's principle any term in the Lagrangian function indicates the existence of effects which are the same as those forces parallel to the axes coefficients which would be produced by electromotive of x. cr. .. d . and e. =e  h are controllable coordinates. taken. <r . + d . through planes of unit area at right angles to the x.. the coefficients (MI) are functions of d where <rx . y.(frSl) ~T (vx f) ' yt>l ' dz^ dx^ dy^ Then. g. g. y. A. d . since f. volume of the substance due to sensible heat. z.... 7 . f } g. The coefficients (uuj are supposed not to involve /. . d^'fi+Ty^ 'fc^ y. .
... we may put and then (127) may be written So that by Hamilton's principle if unit length which would produce the term indicates X be the force per effects as this same To take the simplest case e.Since S< = if (<rjf) + fofc) + (126) (<rM).bz b _. As $e/a is the alteration in the energy made by the . let us suppose that /(e) is a linear function of so that /(e) = a 4. f () J  ' *r / (e) \ JTT T~ _._ T^ / a+ be. : onrl CtLIVJ.} proportional to the temperature. we see that we integrate by parts the terms in Sf are Since is 3 ^/(e) {(z^)' zi + .
. So that this term indicates the existence of an electromotive and proportional to the rate of alteration If of the temperature in that direction. ' v b and a remain constant throughout the substance.x Y have Y ~ Z. . 54. Thermal is effects of this term.x fl~. \ d /i \bv dx\a j I (128). b$  a ay dB  a dz occurrence of Sf in the surface integral shews that there is a discontinuity in the potential at the surface of separation of two media and that the potential in the first The medium is higher than that in the second by a J2 where the suffix attached to the bracket indicates the medium for which the value of the quantity inside the bracket is tobe taken. Let us suppose the quantity of heat that must be supplied to^ unit volume of the conductor to keep its temperature from that 8(2 changing when a quantity of electricity Sf flows through it. crv y ~ (7.ana tnererore X~ or if a. and Zare the electromotive forces parallel to y and z respectively we force parallel to.
=If ov ' v" a ax /" by equations 127 and 129. $Q will have the same sign Hence if as <rj>. had a negative specific heat. case the electricity behaves as substance. If we produced a distribution of electricity throughout the volume of a body.and independent of x. . wl/^_. then we may suppose that o^ vy fr.temperature constant when a current flows into that in this it from a hotter place. since ft and u are necessarily positive.. Let us take the case of an isotropic body whose . so that *Q = ~v *a u ~fa ^1 ( J 3)is If the current flows in the direction in which heat flowing. Hence crx b is of the opposite sign to the specific heat of electricity in the if it see from equation (130) that the electromotive force at any part of the circuit always tends to produce a current in the same direction as one which would cause a fall in We temperature at this part of the circuit. are each equal to o. y. to u be the current parallel x and Sf the time it has ~been flowing 8/=8f.I#\ n <& . dK\ . that carries cold is a current from a hot to a cold place so with it. temperature is uniform. some very peculiar results would follow if this term existed. then ^/w^/. z. that is from hot to cold. unit volume to keep <rj> is positive heat must be supplied to the .
.+ r=P' dz ay to the So that the energy in unit volume corresponding heat energy equals 3 uu)'u +. we may suppose. The case is quite analogous is to that of a moving body the effective mass of which suddenly increased... To altered calculate the alteration in temperature if amount and even the sign of this we must observe that it. since ^~^' that it _dT will be of the form where /(# Rrr* ^) denotes a quadratic function of v lt vs 0.. ivli^h rlnes not involve As this expression is pro . (131). and thus when we the alter the volume density of the electricity we alter energy due to the heat and therefore the temperature....} .. will be we suddenly alter p... by the tightening of a momentum constant. string attached of the system and not its velocity which remains we of the express the term (131) in terms v ...df 7ax + dg dh r... corresponding to the various coordinates 11^ momenta us we ... see. v .. If In this case it is' the to another mass..
Let us SUD . Hence we see that the analogy between the behaviour of electricity and that of a fluid possessing either positive or negative specific heat can be extended electricity to is cover the case when the a bodily charge of communicated to body. The by equation (130) the "specific heat" of value of this for antimony at the tempera5 ture 27 C. when the the E. io~ of the E. We must now find a limiting: value for So. that is the electricity behaves like a body whose specific But we saw that b<r was of the opposite heat was negative. Now fSbvIa electricity. of a Grove's cell about 2 x io 8 in absolute measure the "specific heat" of electricity in antimony in absolute measure will be about 6000. For multiplying both sides of equation (132) by /?. sign to what Sir William Thomson has defined as the so that if bo increased specific heat of electricity in the substance. is (see Tait's Heat. M. unit is F. can shew however that if the charge of electricity be same order of magnitude as those which occur in electrostatic phenomena this heating effect must be exof the We tremely small.is positive the . p. approximately. by communicating a charge of electricity to it.temperature of the body is. we have u = is (I Sp. As M. is F. 2 180) about io~ x 300 of a Grove's cell.
I X lo 10 ' 7 mechanical equivalent of heat. . so order 2 . ' 111 Now so that __ j = 9 i x" i io a<T ' __ Hence substituting this valu P nf f temperature 2 fC J350 * s p for S^' we get at the = 2 x 6 x 10 9 x 10" x __ ? lo'V P%e is th< temperature.irpr .
let then us suppose that the strain e is an extension of a if a be the displacement of a point along the do. nor in a wire where the strain is constant by any variation in the temperature. If this is so then we are led to conclude that b is a of electricity to an unequally heated rod it communicating a volume distribution must tend to strain For wire. Now if we have a closed circuit made of one metal.acting along the wire. change in the Lagrangian function isotropic when the medium is d . experiment. then the integral of the expression taken round the circuit will vanish if either 6 or e is constant all along the circuit but will not in general vanish circuit. wire ds If a be increased by Sa. the coefficient of Sa in the is. and hence function of the strain. if both and e So that we cannot produce currents vary round the in a wire whose temperature is constant by any variation in the strain. while on the other hand we should expect to get currents if both the strain and the temperaAll these results agree exactly with ture were variable. ds being an element of its length. in which cr v may vary with the temperature and state of strain.
then we see by (114) that from considerations about the heat developed we can only derive information about the part of the electromotive force which depends upon temperature and cannot tell anything whatever about any other part. be twisted when is electricity is distributed 56. If Thus when an unequally heated wire has electricity disvolume there will be stresses tending we consider way that twist instead of elongation we can show Avill in a similar an unequally heated wire through it. The amount of knowledge of the electromotive force which we can derive from thermal considerations is however limited in a Avay which I think is generally overlooked. see by 47 that when a coordinate x is increased by $x. the heat (? which must be supplied to the system We to prevent its temperature from changing is given by the equation where X is Now let X be the force of type x acting on the system. As a particular application of this principle we see that the Peltier effect can throw no light on the absolute differof rmfpntinl hpfurp>n two rKffprprit mptnls and hence . The electromotive force in a thermoelectric circuit parts of the circuit generally calculated from the heat developed in various by the passage of the current. tributed throughout the to strain the wire. an electromotive force in a thermoelectric circuit and x a quantity of electricity.wire.
J3. Etting hausen and Nernst (Wiedemann's^wzrt/e#. y. 57. y the components of magnetic force parallel to the axes of x. the components to this effect will if the laws we have just quoted are true be given by the expressions JO ( < ( d& dd\ r pj dx a \ dy] . magnetic force. 1887) have recently discovered an electromotive force due to inequalities in temperature which is very analogous to the Hall effect They found across a thin plate electricity. 737 and 760. if The direction of the elecplaced in a magnetic field.medium. ities of Electromotive forces produced by inequaltemperature in a magnetic field. and a. v. z of the electromotive force due respectively. it is made is flowing of a substance which can conduct that when heat electromotive forces are produced in the plate. represents the temperature. xxxi. This electromotive force If is especially large in bismuth. tromotive force is at right angles both to the magnetic force in direction which the and to the temperature is changing The magnitude of the electromotive force is proportional to the product of the magnetic force into the rate of increase of the temperature at right angles to the lines of fastest.
Let us consider the term where f. The variation of this term when/ is increased by Sfis where /. n are the direction cosines drawn outwards of the normal to the surface enclosing the volume through which the integrals are extended. z respectively. g. By Hamilton's principle the term in the surface integral .We shall now proceed to see what term in the Lagran gian function would give rise to forces of this kind. y. h are the components of the electric displace ment parallel to the axes of x. m.
and /. y. By the same principle the terms in the volume integral indicate the existence of an electromotive force throughout the body whose components per unit length parallel to the axes of x.( dB dB T dz ^ \Tdx Qlp^a dy) K is the specific inductive capacity of the substance.where corresponding quantities indicated in the media (i) and (2) are i and 2 respectively to the symbol representing the quantity. dx dy) these are the expressions for the components of the electromotive force discovered by v. Ettinghausen and Nernst. u are the direction cosines of the normal drawn from medium (2) to by affixing the suffixes medium (i). m. z are a 3 dO dz dB 7 { ydx (134). . These forces do not will therefore satisfy the solenoidal condition electricity is . they produce a distribution of throughout the substance whose volume density p tion given by the equa P47T d& 3~ \_dx dB dz] T d Tr dy d9 ~T dz d6) T\ dx) + where d .
We can see by equation (113) that SJf the heat required by volume to prevent the temperature from changing when a quantity of electricity 8/ passes through it parallel to unit the axis of x is given by the equation of the electromotive force which 8Jf (that part arises from the part of the energy corre sponding to the sensible heat) Sf . if u. z respectively and t the time the displacement are the w then since we have . when quantities of electricity Sf. to the axes of x. v. O a. z respectively then so that 8/i pass parallel dy or. v. Sg. components of current parallel to the y. u. w are the components of the current. axes of x. y. \u dx [ v J + w d6\ j. ^\ W 1 dy) \ .ff dB O d@} a . thus the part of Bff which arises from this term is given by dd . J ^ dz)" \~dz ^dxr^dx "dy. Thermal phenomena arising from this term. dy dz) where 58.or neglecting QP = KQ f dB 4 dB ..Y. {R dx ( . takes. f d@ _ ^\ V JL .
737 760. 1887). equations with (135) we see that ax So that if ay az) the action of the mechanical force on the current tends to make move (2 is in the direction in the substance conveying the current which heat is flowing. If we apply to the term dx dy dz . then when negative. unit time to unit volume to prevent the temperature from keep changing is given by the equation Sff  <2 {resultant mechanical of force on x unit volume x flow of heat cosine the angle between these two quantities}. pp. heat its must be abstracted from the substance to temperature constant when currents of electricity And the heat which has to be supplied in flow through it. Ettinghausen (Wiedemanu's Annalen. Magnetic effects of this term. Heating effects in a magnetic field have been detected by v.where //. 59. is me magnetic peimeauuuy. xxx.
~ X ~ 4* 7 7 n ^ We see that the equation is no longer true. z respectively are (136). the distance between the points x. z and If is a point at which there is an electric dis77.04 where X~ ~~ 1 dp _*. y. then as before the components of the magnetic force parallel to x.) 'dr\ .at . JJ d/i\ i d ""^ i f (dh i( df\ I d \ i LI L V** ( y/ \Uv\> i*/s/ + where r is I ( < it/ ~~ d** \ d tt T T T axayaz. placement. dy dt] dt^ dt.(l^ l^n/^/^ 3 4? dt] \d\d$. y. but that now dk\_dfd_e___dfd6_dfde\ d^j d^.
Thermal effects accompanying changes from this term. . effects. then. according to MaxTheory of Light. 6 1. Since in magnetization. (114) be accompanied by reversible If the intensities parallel to the axes of z be increased by 8A. SC" respectively. small. Ettinghausen's and Nernst's phenomenon produce . changes in the intensity of magnetization must by equation thermal x. SB. if Hall's Rotation of the plane of polarization proRowland has shown that effect exists in dielectrics. the plane of polariza well's Electromagnetic tion polarized light will be rotated when the dielectric through which the light is passing is placed in a magnetic field the lines of force of which are more or of plane less parallel to the direction of propagation of the light. then by the mechanical equivalent of die heat equation (114) SH which must be supplied to unit volume to prevent temperature from changing is given by the equation its *A*W + \ r. arising the magnetic forces expressed by equation (136) arise from that part of the kinetic energy which corresponds to the sensible heat. duced by the flow of heat. j>. shall We of now proceed to investigate whether the existence will v.however that these forces are exceedingly 60.
neat
is
nowing.
Let us suppose that we have a circularly polarized ray of light travelling parallel to the axis of z through a dielectric in which there is a uniform flow of heat also'
parallel to
z.
Let
/
and g be the
electric
displacements parallel to
the axes of
x andjv
respectively,
and
of the vector potential parallel the components of the electromotive force and
J^and G the components to x and y respectively,
X
F
parallel to these axes,
then since dOjdx, dQ\dy both vanish
^^
X&QP*,
dt dz
T/
.
dG
_
dB
,
Qa. ^ F=j,+ dt
dz
;
where a and
parallel to
fi
are the components of the magnetic force
respectively.
x and y
if
Hence
K be the specific inductive capacity
4 7T y ^
K*
dG  dB + Qa. ^ dz dt
7
with respect Differentiating the first of these equations
to t
we
get
but in a dielectric
if
we
neglect
Q we may
2
put
dt
dtdz
'
where /x, is the magnetic permeability of the dielectric. Substituting these values in equation (137) we get
~
\j.K dz"
df
ju,
dz dtdz
^
''
For a
circularly polarized ray
we may put
z)
F= A sin rA
(vt
GA cos
*
^
27T
where
the velocity of the light, and A. its wave length. Substituting this value for F'\~& equation (138) we get
V is
_L = ~"
yu,JT
=_^^ dz
/x,
'
and thus the velocity of the ray temperature had been uniform by
1
is
greater
than
if
the
Q
fJL
d9
dz
2
velocity of propagation of a ray circularly polarized in the opposite sense will also be increased by the same
The
amount. So that regarding a plane polarized ray as made up of two rays circularly polarized in opposite senses we see that when' such a ray passes through a medium in which
there is a steady flow of heat, the plane of rotation will not be rotated, but the velocity will be increased by
rature of
iooC.
would only amount
per millimetre, the change in the velocity
to
x 13 x io a
or
65,
7 only about 22 x io~ per cent, of the velocity
change is of light, and
therefore
is
this
violet
light
would have
to
traverse
about
20,000 c.m. to gain or
much
a wave length. This effect too small to be detected experimentally.
lose
equation (135) that when electric displacein a field in which the temperature is not uniform, heat is absorbed or evolved, so that we should
We
saw by
ments take place
expect thermal changes to accompany the propagation of a ray of light through a medium the temperature of which was not uniform.
(135) the heat 8J7 which must be supplied volume of the medium to prevent the temperature changing, is if the heat is flowing along the axis of z, given by the equation
By equation
time
in unit
to unit
Let us take the case of a plane polarized ray
for
which
approximately
/ A cosT A (z//0)
heated
So that the propagation of light along an unequally medium would if this theory is correct be accompanied by periodic emission and absorption of heat, analogous
accompanies the propagation of sound according
to that which
to Laplace's theory. According to Maxwell (Electricity and Magnetism, Vol. n. p. 402) the maximum value of /3 for strong sunlight is '193 so that
4irvA
=
2
'193,
and therefore
STrV.,4
let
=
02,
H
us take A as 3^9 x io~
in air
* rr SJ7=
6
the wave length of the violet ray
27r
27r dO /I x <2 x cosr5 x ioj
/
j.
\
(vt
z)
/ j \ smT (vtz).
If
Q
there was a
were as large as it is for bismuth, i.e. '132, and fall of 100 C. in one centimetre, then the
of heat absorbed or emitted would be
33 x io
3
;
maximum amount
would correspond to changes of temperature of not more than one ten thousandth of a degree centigrade, if the specific heat of the substance were as great as that of
this
water.
62. Longitudinal effect, v. Ettinghausen and Ernst found that in addition to the transversal electromotive
was a longitudinal one along the lines of flow of the heat, which was not reversed when the magnetizing force was reversed, and which was proportional to the square
force there
this
If we consider the effect of square of the magnetic force. term magnetically we shall see that it indicates that the
magnetic permeability of a magnet will be afifected by the proximity of a conductor throughout which electricity is
distributed.
It is interesting,
63.
because suggestive of new physical
in the
phenomena,
to trace the
consequence of the existence
Lagrangian function of terms, which are symmetrical functions of f, g, //, a, (3, y and their differential coefficients,
such as terms proportional to
.da.
te*.
s
&
dB
h
7
dy
fc
*
df Q dg + dh P T y jT + ^ dz' dx dy
'
f \Tz~ dy\
d _d j\ ( ds _
dy) \dz
dy ~
A dz
M\
"dy)
_ + f^y _ ^\( \dx dz) \dx dz
dx) \dy
dx;
The
no
reader
however who
is
interested in this will have
of these terms by difficulty in tracing the consequences the methods already given.
CHAPTER
VIII.
ON "RESIDUAL" EFFECTS.
64.
THERE
it
are a great
many
cases in
to
which the
appli
cation of forces to a
it,
from which
produce a change in does not recover for some time after the
body seems
forces
have been removed.
fibre twisted for
if we keep a metal wire or glass some time, it will not when the twisting couple is removed at once vibrate symmetrically about its but will oscillate about a original position of equilibrium,
Thus, for example,
.
new
zero
zero which
maximum
gradually approaches the old one, the difference between the temporary and the true
and the time which elapses before these coincide increasing within certain limits with the duration of the
original twisting couple.
Phenomena
"
of this kind are called in
German
treatises
elastiche nachwirkung."
This peculiar effect of torsion
does not seem to have received a
in this country, but the analogous cases in electricity and magnetism are called respectively "residual charge" and "residual magnetism."
name
This
latter effect is
only partly analogous to that
the motion of th machine being resisted by a frictional force proportion We shall suppose at first that the mass to the velocity.. first Then the only extern force acting on the system. B..LU uc auic LU icuuu lib ma. but not the with respect to the time..f(xy) =px + 7y.. .jjueusm iijr uj length of time.. and that the connexion between the two machini is expressed by the existence in their Lagrangian functic of a term /(.ay/) which involves both x and differential coefficients y. the second machine is so small that its inertia may 1 neglected. We have a shall now endeavour to the case of the twisted wire. (140). frictionless to find a dynamical analogi Let us suppose that \ machine whose configuration is fm by one coordinate x and that this is connected with anoth machine fixed by the coordinate y.. where a. If x and y are small we may put ... the equations of motion will I of the form the force X acting on the machine is = X . y are constants.
70. equation (145) is not convenient. 275. zu Wien. p. In many cases we are given the forces at the time f and not the displacement. connexion with the second is to make the forces called into play at from its position of equilibrium any time by the displacement of the system depend not merely upon the displacement of the system at that time but also upon the previous displacements.r) Monatsberichte. 141) has shown that assumption that \j/ (T) is proportional to <T kT agrees with Neesen ("Elastiche Nachwirkung bei Torsion.~+(ay)ypx = v The solution of (143) is (143). 1874) works out a theory where ^ (T) is proportional to i IT." Berlinthe his Boltzmann (Sitz. 1874. Ct  P^d!2 ' (l44)r substituting this value of y in equation (142) we get We of its see by this equation that the effect on the first system. Feb. and that a displacement x lasting fora short time r produces after a time a force rxijf T where 02 _ (<L. and in these. If as is generally the case the motion is so slow . Akad. k.. 12. p. der experiments on the twisting of wires.
. b 7 / \ ) (fJL a) and thus when the external force is removed If the primary machine had been connected with sev secondaries instead of with only one. displacements are given we should have.so that and therefore y=* ' O . Jo b (/*) ) the forces are given r l> (p. This is the general express for the residual effect in terms of the forces acting on for all the system when it was under constraint. If we cannot neglect the inertia of the secondary syst . if X= and if I X l2i jr I  / Ut . and the sum ta) secondary systems.a) j (146) where OT is written for 2 /3 /^ (/A  2 a) .
the arrangement of the molecules of the glass . and may suppose that during the actions of the electromotive force on the glass. For example in the case of the residual charge of the Leyden jar we may look upon the electrical system as the primary system and the system consisting of the molecules of the glass as the secondary system. and the general solution is of the form where c is a constant which depends on the constitution of the secondary system but not upon x. into Thus the introduction of inertia the secondary system does not change the form of the solution. 65. In those cases in which residual effects occur we that the secondary systems which are affected "by the changes in the primary are the molecules of the body which is the seat of the phenomenon or a portion of such may suppose molecules. it only introduces fresh terms of the same type as those which previously existed. This is the general expression for the residual effect in terms of the initial displacements.y= where \ and A 2 are the roots of the equation J3X S + l>\ + a y = o.
"The condition of must depend .is most instructive on this point. the strain in which is either zero or at least less than in the original configuration. "We know that the molecules of all bodies are in motion. We may in this case assume that in every second a certain proportion of these groups . so that if we consider a certain group its configuration is never very different from a certain stable configuration about which it oscillates. even in a homogeneous in this respect. this breaking up of a configuration partly on the amplitude of the oscillations and partly on the amount of strain in the original configuration and we may suppose that different groups of molecules. are not in similar circumstances "Thus we may suppose that in a certain number of groups the ordinary agitation of the molecules is liable to accumulate so much that every now and then the configuration of one of the groups breaks up. certain mean of the molecules merely oscillate about a position. In gases and liquids the motion is such that there is nothing to prevent any molecule from passing from any part of the mass some. to any other part . solid. "This will be the case even when the solid but if is in a state of strain provided the amplitude of the oscillations does not exceed a certain limit. and this whether it is in a state of strain or not. but in solids we must suppose that at least.. it does not tend to return to its exceeds this limit the group former configuration but begins to oscillate about a new configuration of stability. of molecules.
" But we may suppose that there are other groups. also helps to explain the state of the rsolid after In this case a permanent deformation has been given to it. as consisting of . "Now if such groups of greater stability through the substance in such abundance solid framework. increase of moisture. and this limit may be different for different systems of these groups. "This view of the constitution of a solid. then when a strain is .gradually diminish as the groups of the applied the resistance to it will first kind break up. some of the less stable groups have broken up and assumed new configurations. violent vibration. itself.groups of molecules some of which are in different circumstances from others.and also groups of the first kind which break up of themif "But selves. the configuration of which is so stable that they will not break up under the ordinary agitation of the molecules unless the average strain exceeds a certain limit. but it is possible that others more stable may retain their original configurations. the substance will be a not be permanently deformed except by than a certain given stress. so that the form of the body is determined by the equilibrium between these two sets of groups but if on account of rise . is . it will not at once return to its original form but will only do so when the groups of the so often as to get first kind have broken up back to their original state of strain. of temperature. are disseminated as to build solid up a will which a stress greater the solid also contains groups of smaller stability . or .and this will go on till the stress reduced to that due to If the body is now left to the more permanent groups.
66.5^(6 y 777 < I k(tT~] k(tT\)\ /T/t8^ We see from equation (147) that will secondary x never change return slowly to its if we have only one but that the system will position of equilibrium and never get sign. Thus if we give a fibre a strong twist in the positive direction for some considerable time and then a twist in the negative direction for a short time. acts. beyond fibres it whatever may have been its previous history. the residual torsion after the twisting couple off is taken may be first in the negative and then in the positive . We know however and effects that in the case of residual torsion of glass the residual charge of a Leyden jar the residual may be made to change sign.aetormation. then we have by equation tt (146) :k (tt'} Xdt' If the ries instead primary system is connected with several secondaof one then we have ') A= . acts on the system from Let us suppose that the force /=o to t= T. Let us now apply equation (146) to a definite case. and that from t=T^ to /= s the force J^ X l T .
inertia of the Using the same notation as before and neglecting tin secondary system we have for the free vibra . cit. We now investigate another effect due to th same cause as the residual effect but of a different kind ii This is the effect of the secondary system on the way which the free vibrations of the primary die away. Dr John Hopkinson represented the residual charge c alternations in a Leyden jar art. the effects of the inertia of the secondary system we got twc but only two values of k for each secondary. ary system.and since after the external force is removed is not a function of t. can be representet by a single term of the form ct~ kt shall 67. This is According to Neesen torsion in silk (loc. we see that the sign of the residua effect can only change once however complicated th the signs of the twists or electrification previously applied to the system may have been. 40 and he showed that for the formula to agree with hi experiments on the residual charge in glass it was necessar Now when we include) to take more than two values of k. p. Encyclopedia Britannica.) the residual effects o and guttapercha fibres . so that as w have to introduce more terms than two to represent th residual effect in glass we must have more than one second an indication that glass is not a homo geneous substance but a mixture of different silicates. by a formula of the same type as (149) (se ChrystaPs Electricity.
there is no secondary system.or say eliminating y we have As as this is a linear is &. when . and if the in the period residual effect does not produce a large change of the equation of vibration we may on the right hand side substitute i. then/ that equation let us assume given by the equation x varies or The right hand side of this equation is small.e. i for/ its value a'. substitutions [pi A}* and for a making these we have or A ^ So that 2 a? or if y8 be small .
where exp (x) = e So that the ratio of the amplitudes of two successive v . d sx . ii Now be if the motion of x were resisted by a frictional force proportional to the velocity. in (151) Substituting this value of of the two amplitudes the expression. and is given by the equation. the equation for x would . dx the solution of which is * = Ce where _ ^ cos two successive swings w C and is e are constants. swings is where T is the time of a complete oscillation. we get T for the ratio y h p tf I ' __ \ Aaf + _ . The ratio of the amplitudes of in this case . /> f T=2Tr{Al^Y approximately.
jy is amplitude connexion with the secondary system.altered.l A V A 7T A r\ .smaller than p^/a the rate of decay would be increased instead of diminished by increasing the vibrating mass.greater with the longer periods than that calculated according to the law of square roots from its amount in the experiment with shorter periods. as he found that the loss was . if the decay in the oscillations This agrees with the results of Sir William Thomson's experiments on the decay of the torsional vibrations of wire. In fact if A were much 2 . the successive amplitudes is When the decrease in the due to the of two ratio exp I so that the logarithmic decrement when the resistance frictional varies as is when it is due to the secondary system i it varies as Hence we . as = the rate of decay has its maximum value when A . the variation see that if the mass of the vibrating body is of the logarithmic decrement will be less in this case than it would were due to friction.
while in the cases we have been able to follow in all detail the in previous most all of that the quantities introduced. So far we have been dealing with phenomena in which as in ordinary dynamics the quantities concerned were mainly of a vector character. or the number of molecules in a particular state. We shall now however go on to to consider phenomena when are chiefly scalar. The chief difference between these cases and those we have been considering isthat in these we have as in the kinetic theory of gases todeal chiefly with the average values of certain quantities and cannot attempt to follow the variations of the individual members which make up the average. INTRODUCTORY TO THE STUDY OF REVERSIBLE SCALAR PHENOMENA.. dissociation. the quantities we have deal with such as the phenomena of evaporation. In changesthese new cases we can get by the application of the Hamil .CHAPTER IX. chemical combination. vapour density. where the quantities Avhich have to be considered are such things as temperature. etc. 68.
and the magnetic configurations are under our control and have therefore been called ( The coordinates fixing 46) controllable coordinates. we can fix its geowe can within certain limits strain it in any please. The systems we shall have to consider are portions 69. way we we may establish electric currents or electric displacements through it. 70. The relations we when the body is in a shall deduce are those which exist steady state. we have called these unconstrainable coordinates. of matter in the solid. the strain. the positions of the several secondary systems are not however within our control and we have not the power of altering any one of them .UC. and if the y^nr>rr!inaf(= AntArc pvnlirif'Kr info tVi P PYnrPCSl'ntl fnr .UI. all that we shall assume is that the mean values which we can observe and which depend upon the unconstrainable coordinates are steady.CU jjuiui ui view.IX. and if the body is magnetic we can magnetize it within the limits of saturation so that the : coordinates fixing the geometrical.J. control a primary system in many ways. of a very large number of secondary systems or molecules. number state is When we say that a system consisting of a great of molecules is in a steady state we mean that the steady with respect to the controllable coordinates as to whether it is so or not with and make no supposition respect to the unconstrainable ones. the electric . and consist. liquid or gaseous state. Now we can metrical position. according to the molecular theory of bodies. Thus when the system is in a steady state the velocityof each controllable coordinate must be constant.
 d ^ Remembering Lagrange's Equations equation reduces to we see that this dL dL 1 T q. y V V<b s Y 1 / \ Let us suppose that the symbol of variation refers to a disturbed motion in which the values of the controllable coordinates are slightly altered while the velocities of the speed coordinates remain unaltered and constant during the disturbed as well as the undisturbed motion. which apply to them are 72.A t r dL\^. rf/ ^{^(dL +S j I ( )t. Let us denote the controllable speed coordinates by the symbol q i: the controllable positional coordinates by <? 2 and the unconstrainable coordinates by q..\dq. We three shall for the sake of greater clearness consider the terms on the righthand side of equation (152) separately. A o^ y ..value so long as the velocities of the controllable coordinates are not altered. as the considerations different in each case.A then we have by the . Let us first take the term .(152). IA ^> dt dqj .. Calculus of Variation a dtdqj i" 8^ *^ dL\s ) d .
J JL 1 KJ. Mag." Phil. They do not therefore contribute anything to the mean value of Z. Heat. XLII. vanish. 178.IIH. Since qs is not a speed coordinate it must enter explicitly into the expression L. so that when the motion is steady the velocities of coordinates of this class. To show that the terms ~dL t vanish we must use paper "On the the reasoning given by Clausius in his Second Axiom of the Mechanical Theory of p. 74.generality suppose that the coefficients of terms in the kinetic energy involving the velocities of positional coordinates are all zero this and that therefore 2 2 may be put equal to zero. Let us in the first place consider what the coordinates . We shall now show that the term also vanishes. 73. In are considering in the expression for the variation of the mean value of the La way we may see that the terms we grangian function vanish.J'V and thus the term we are considering vanishes. and so we may without loss of. The terms in L which contain the velocities of is positional coordinates always vanish when the motion steady.
some not increase with the time. produce a change in each term of Now any change which we have the power in . to produce any of the coordinates fixing the system will. while that of the former will not be so in consequence however of the frequent collisions . cooruuiaies uxiag me pu&uiuu ui me of the latter relatively to their centres of mass. since the motion is steady. The motion coordinates will be periodic. this times negative. so that if the position of a molecule be arbitrarily changed the distance between the disturbed and the undisturbed positions will not increase indefinitely with the time. the difference will sometimes be positive. for these coordinates will and therefore the part of depending upon these coordinates will fluctuate between tQ increases.secondly. but will fluctuate between limits which do Thus if q^ is a coordinate of kind will fluctuate between positive and negative values which do t fr still not increase with the interval The same reasoning those coordinates which relatively to its oscillate will fix apply with greater force to the configuration of a molecule centre of mass. between the molecules their direction of motion will be continually reversed. limits which do not increase as the time if.
be produced by slightly altering the values of the coordiWe may conclude that one second is a sufficiently long interval over which to integrate since according to the molecular theory of gases there are both a great many collisions and a great many vibrations in this period. We can prove however in this case that the modified Laeraneian function CS n) is stationary when the system is . In the above investigation we have supposed L is expressed in terms of the velocities of the coordinates and the proof is only valid when it is so expressed and does not hold when the that the Lagrangian function velocities corresponding to some coordinates are eliminated and the momenta corresponding to them introduced instead. sufficiently long.g. so that when the motion is steady we have 8(Z) = o (153).long interval we may neglect any terms on the right hand side of equation (152) which fluctuate between fixed values and therefore as far as coordinates of the kind q^ are concerned put //! 8 I Ldt=o. and where the variations are such as could nates. this is Jio when the interval t^ t is We have seen however that also true as far as the variations of the other coordinates g l} y^ are concerned. e. where L denotes the mean value of L taken over unit time. one second. 75.
X the force of type is x which must be applied to maintain equilibrium given by dL *=&' where L is the Lagrangian function or its modified form .a to preserve equilibrium. 76. steady state. and since d_dIJ__ dt dq Ave dL _ dq have by the Calculus of Variations where j> is the momentum eliminated coordinates.the other coordinates. of the ordinary Lagrangian modified form according as it does not or does contain the momenta corresponding to some of the is L the mean value function or its coordinates. Fortunately however this knowledge is unnecessary if we calculate the Lagrangian function from the forces required For when the system is in . would sometimes be occurring in In the physical applications of this principle it difficult to tell whether a symbol L represented a momentum or a velocity. that the right We corresponding to one of the can prove exactly as before to hand side of equation (154) vanishes for all variations in which the momenta corresponding the eliminated coordinates remain unaltered. Thus we have where in all cases an equation of the form SZ = o.
When energy the is system is acted on by gravity the potential is mgl cos 3 so \ml* that the Lagrangian function 2 sin 2 30 + mgl cos 3 which may be written jdd and .mP sin 3 cos 30 2 .sin $< 2 2 . + mgl cos 3 possesses the property of being stationary. let Thus to take an example is us consider the case attached to a fixed of a heavy particle whose mass point by a string whose length m /. is and moving so that the string makes a constant angle $ with the vertical. where $ and the angle which the plane containing the string a vertical line makes with some fixed plane. it refers is in a steady state. If however the Lagrangian function is expressed in this terms of $ the momentum corresponding to 2 tf> and given by the equation $ = ml sin 2 $<j> the Lagrangian function becomes . is the expression for the terms depending on the controllable coordinates in a function which possesses the property of having a stationary value to when the system which 77.XJJ the sura being taken for all the coordinates and ^expressed in terms of them. kinetic energy of the system is The mC. The couple is @ which must act on the system to keep 5 constant is .
_ . when we By the Calculus of Variations d dL\ . is of stationary or $. cos o 3 ml* sin 3 r\ 1 we see that the "modified" Lagrangian function again equals 4 Id6 Thus the expression mgl cos &. fdL w _Vi . If 78.i in terms of and <3> rf\~ >*: .. <j> however may be expressed.P" cosec $ + mgl cos &. Since equals however when expressed i . whether in terms This example illustrates the principle that if we calculate the Lagrangian function from the forces necessary to preserve equilibrium we need not consider whether it is expressed in terms of velocities or momenta. we consider the proof by which the equation was established we shall notice one point which we must are calculating the value continually bear in mind of the potential energy.
dq dt dq Now in ordinary Rigid Dynamics is perhaps the most usual form of Lagrange's equation d dL ~dt dL _ ~dq~~dq~^ where this Q is coordinate. energy we are conwhich produces Lagrange's equation may now be written dT . and equation (153) is true. Thus to take an example. assigned external put LT is If however we are i^ where to use equation (153) we must that we must add to the potential sidering the potential energy of the system the external forces. the external force of type q tending to increase = Avhere is the In this case L T V V potential energy when the coordinates have their value and the system is free from the action of forces. respectively/ h is jv \J ' t> f and that the equations of equilibrium are .^(T^) = o. of x y : . in Electrostatics' we often of unit volume of a assume that the potential energy dielectric whose specific inductive capacity is ^Tand through V which the z are electric displacements parallel to the axes g.
If considering however we wish we must put to apply the theorem we are n< for then the equations of equilibrium are dV^ ~df __ _dV ~ _dV_ ~~ ~ ' ~dg ~dli The necessity of choosing motion are of the form V . .n n ~\ t one to which we must always be alive in dealing with subject. so that the equations d dt is dT dq~ d dq (2 ~ js\.
and Lagrangian function which do not involve these quantities if we require these we must determine them by other . SINCE we can observe and regulate the forces of the types of the "controllable" coordinates we can determine how they depend upon the values of these coordinates and then by means of the expression (155) calculate all those terms in the mean Lagrangian function which involve such There may however be some terms in the coordinates. magnetic or elastic configuration of the system. X.CHAPTER FUNCTION. THE CALCULATION OF THE MEAN LAGRANGIAN 79. and in the terms depending upon the strain coordinates we may include . In the expression for the energy we can calculate all the terms involving the coordinates which fix the electric. considerations a large solved even though terms. number of problems can however be we do not know the values of these the different kinds of terms which let us To may get some idea of exist in the Lagrangian function consider the energy of a system consisting of a large number of molecules.
potential energy of the molecules may also contribute terms to the Lagrangian function which do not involve the controllable coordinates by equation (155). value of the Lagrangian function for a perfect gas. The methods some gas.The sum of these contributions will be proportional to the number of the molecules and must also be a function of the temperature. absorbed or evolved when the change takes place and know the change. if any. Mean 80. Lagrangian function its and which therefore we cannot calculate For the purposes for which we use the all that we require to know about it is when the system is changed in some Now if we measure the amount of heat definite way. so that the only The quantity they can depend upon is the temperature. which takes place in the kinetic energy. Let us suppose that unit mass of the gas is enclosed whose distance from . Lagrangian function of calculating the mean value of the will be best illustrated by working out Let us begin with that of a perfect particular cases. we can calculate the alteration in the part of the the change in value potential energy which is independent of the controllable coordinates. because the mean state of the system is fixed by the controllable coordinates and the temperature. and the mean kinetic energy must therefore be a function of these By hypothesis the terms we are considering do quantities. in a cylinder furnished with a piston. not involve the controllable coordinates.
.*> . where p is the pressure of the gas and A the area of the piston. Now so that dx _^ v dx in so far as Integrating this equation we have ^T depends upon v and 6. the absolute temperature and R a constant such that RO equals the square of the velocity of sound in the gas. But if the gas obeys Boyle's law where v is the volume of unit mass of the gas.If H denotes the mean value of dH ' the Lagrangian function of the system. the mean value of the force of type x produced by the system when in a steady state is by Lagrange's equations dx Since there is equilibrium between the pressure due to the gas and the external pressure dH A &.
.. (158)..... This is the Lagrangian function for the gas itself. (0) it may be included in the first term.. (159). when we consider the phenomenon is of evaporation.. Thus for unit mass of the gas or if p be the density of the gas We shall see later on... as this is the part of the potential energy which depends upon uncontrollable coordinates. it also includes that part of the kinetic energy which is expressed entirely in terms of unconstrainable coordinates. when an external pressure acts upon it we must add to this value .... for this can be included in from its the term f(&) to complete its value we must subtract it iv the potential energy of unit mass of the gas when ... as we may regard vg as f / quite arbitrary. particles are infinitely distant from each other.. The Lagrangian function so expression (157) will give the value of the mean far as it involves x.this work that a great many problems can be solved without is linear As far as a knowledge of the value of (0)... If for a mass m of gas whose density is AB+ p given by the equation H= mRQ log ^ + mf(ff)mw P .. that /(0) of the form The is value of 6\o%e .......
/ is coefficient dpIdQ is obtained on the supposition that the volume is constant.So that its pv. Mean Si. .... We must now proceed to find the mean value Jfof the Lagrangian function for a liquid or solid.. so that = dBdx where a (&} \ddj v constant the pressure required to balance this force and a The differential the area of the cross section of the bar. value of the Lagrangian function for a liquid or solid.... mean Lagrangian function is and the Lagrangian function of the two systems is therefore mRQ P log  + mf(0)  mw pV . (160).. Then we have by Lagrange's is equations when the motion steady = mean force tending to increase x produced by the substance. Since adx = dv. Let us suppose that we have a piston whose distance from a fixed plane is x pressing upon a bar of the substance.
where /? is the mean value of (dpIdO] between zero and V 6. is any external pressure we must add to this expression for the mean value of the Lagrangian function of the system producing this pressure. = Where 7 +f 1 (0) an arbitrary function of the temperature. Thus ff=0\ Ji'o pdv + f^ff) say.mO If there f" I /3 JOQ &2 da + mf^ (6) . so that in the expression for If mass of the substance there are the terms this we must subtract w' the potential energy mass of the substance. where p is the external pressure and V the volume of the solid or liquid. will be pv. This. If the mass of the substance is unity where for unit o is the density. Adding this term we get .mw'. Thus in the Lagrangian function for a mass m of the substance there are the terms From of unit . as the in the case of the gas. it is unnecessary to add an arbitrary function of v on integration as this will be included in the potential energy r f (0) is due to strain.
of electrokinetics. is H connected with that of the entropy. rather than the entropy which depends upon other than purely dynamical considerations. and in fact we see from its value for a perfect gas in equilibrium under external pressure that. direct . are those which can often be solved on thermodynamical principles by using the condition that the value of the entropy of the system The value of must therefore be closely stationary. It which has a seems however preferable to use the function H dynamical significance.when rature the body is in V ^ a steady state. The problems which we making use of the principle shall that the now proceed mean value to of the Lagrangian function is stationary. which depend upon the controllable those terms in H coordinates occur also in the expression for the entropy. the change due to any system of electric currents flowing through energy due to this distribution and can be calculated by the ordinary formulae H solids or liquids is the kinetic of currents. when it is it is free from all strain except that inseparable from the body at the tempe we are considering. the change in produced by statical electrification equals minus the potential energy of the electrical distribution. The change in the Lagrangian function to any additional strain or to electrification or mag netization can be at once determined by finding the energy required to establish this particular condition. solve. and when neither electrified due nor magnetized. J. 82. For example. with the exception of the term p V.
to finding the density of a vapour This of course equivalent being the same as that used in So and 81. some of the liquid will be vaporized and is we wish to find how far the vaporization will proceed when in equilibrium in presence of the liquid.CHAPTER XI.. 83. liquid. the rest of the notation before equilibrium is obtained. EVAPORATION. v' be the volumes occupied by the vapour and the mass of the vapour. Then assuming that the vapour obeys Boyle's law we see from equation (158) that the vapour contributes to the expression for ^Tfor the whole system the terms fir. tif^\ . 77 that of the liquid respectively. WE shall is value of Physics. H now go on to apply the principle that the stationary to solve first some special problems in The problem we shall consider is that of finding the state of equilibrium when a given mass of some liquid is placed in a closed vessel from which the air has been exhausted. Let v.
.. (164).to the same expression the terms r.......e r^ + iT/.... has by the equilibrium the value of Hamiltonian principle (75) a stationary value. (163).... Lagrangian function for of (162) and (163) so the Thus ^ the mean value of the is both the liquid and vapour that we have sum * CTQ B sdawr)'w' " . The change in ZTis so that when there is equilibrium we have by the Hamil tonian principle vrWhen S dH liquid diminishes of the liquid is vaporized the volume of the by 8/<r so that we have .... The that small change which we shall suppose to take place which occurs when the mass of the vapour is is increased by a small diminished by the amount Sg while the mass of the liquid same amount. so that in there is When H this state no small change can affect the value of the right hand is side of equation (164)...^)^ ..........
(0) !tl') or since p/o.. (v +v . and therefore dv _ i ~dk~lr Now where for brevity y is written instead of " Substituting for dvjd%.d .._ '\ dH_ where \b ?Po + d^_/ id] is written for a quantity which does not involve write (165) as ^.a/) + ^ r / (5). \ . its value we have .is p^^^W. Since /w = p we m..(w . ~ <zf = 9 log ^+ p ^ p  ? cr . (166). very small we may write this as (w u/) .. Since dHjd vanishes in the state of equilibrium we ha then jR6\og?* = e p^ \jl + (ww) (70 i// (0) .
log/ = 1744324 . 'hence by comparing the other terms these expressions we see that/($) must be of the form AO 84.2795/0 . ether._ I. log/ = 2144686 2743/0 2179/0 42248 chloroform. where A is absolute zero of temperature. + BQ log 0.1. / experiments on the vapour pressures can be represented by the following being the pressure in millimetres of mercury s : water. 6./.17689 log 0. 97. . This form of expression was originally used (Theoric Mecanique de la Chaleur. log log alcohol. in our expression (166) of i/0 in each of these expressions is nearly the latent heat of the substance at the This is is and w it/ the term (w . p. can by the aid of the preceding formulae very easily determine the effect upon the vapour pressure of any slight change in the physical condition of the liquid or vapour. by Dupre. 0. log/ = 125 8852 1684/0. lfi\ _. tii'\ u ^ = n . log/ = 1929792 bisulphide of carbon 3'9is83 log 0. We Let us suppose that the physical conditions are so changed that the mean Lagrangian function exceeds the value we have hitherto assumed for it by x.1729/0 19787 log 0.w')/6 the latent heat at in absolute zero.Then instead of equation (167) 7?fl we have P J7?fi evidently l^n R .) The coefficient \/J?.3'8682 log/ = 1342311 .results or Kegnault of different liquids expressions.
then this process will have to go on further in the changed function increases as system before equilibrium is reached than in the unchanged one. let us suppose that the liquid is a spherical drop. while if x diminishes as increases the equilibrium vapour pressure is diminished. 85.1 62 DYNAMICS. and as the area of the drop . Let us now consider the effect of surface tension upon In order to take a definite case the vapour pressure. Lagrangian any physical process goes on. while if the change in the mean Lagrangian function diminishes as the process goes on shall it will not have to proceed so far. in t^ e which produced the change x function is mean Lagrangian given by the equation the vapour pressure in the state so that if x increases with of equilibrium is increased. This very important principle is a particular case of the more general one system is slightly when the physical environment of a that changed and the consequent change in the mean . this We the have numerous examples of principle in course of the following pages. It will possess in consequence of surface tension potential energy proportional to its area.
since 8p = J?68p. dv' a d ' . i  da JT d = 3 v i i . Now and . / = ar a p . .and vapour the additional So that with our previous notation x = 4 2 T.r therefore =da d\ ~ <z j hence and therefore = 2. we have by (170) 3 ^ _^_r.T tfcr So that if Sp be^ the change in the vapour density produced by the surface tension we have by equation (168) and if Sp be the change in the vapour pressure.potential energy of the liquid there will be in addition to the terms we have already considered the term and therefore in the mean Lagrangian term function for the liquid .
If we have the water in narrow capillary tubes then when it evaporates . .If we take the case of a drop of water if l ff of a millimetre in radius. We can shew that if a is evaporates. we have by (170). the potential energy due to surface tension increases as evaporation goes on. so that thus the mean Lagrangian by the easily the radius of the tube then in this case svi op= 2P cr~ p a T . P We see that the energy due to surface tension makes the Lagrangian function increase as evaporation goes on. then the temperature for is n about io C. function diminishes as the liquid principle of 84 the effect of surface tension in this case will be to stop evaporation and promote condensation. Since the surface tension of the surface of separation of the tube and air is than that of the tube and greater water. so that by the principle given at the end of 84. the effect of it will be to make evaporation go on further than it otherwise would. since RO water vapour is about 1*3 x 10" Sp p 200 13 x io u ' since T= 81 we have fy  = i 2 x 10 6 .the area of the surface of contact of the tube with water is diminished but that of the surface of contact of the tube with air is increased.
. iv.. so that be the change in the vapour density produced by the electrification we have by (168) if Sp .e^jzKa in the mean Lagrangian function diminishes as the liquid evaporates and therefore by the principle of 84 evaporation the will not go on so far as before.' by i 2 _ ' 2K where medium. Blake's experiments on the evaporation of electrified liquids (Wieclemann's Elektricitiit.^. be We In can easily calculate by equation (168) the amount of this this diminution. K is the specific inductive capacity of the surrounding The mean Lagrangian function of the liquid and its vapour is diminished by this amount. that will is vapour density when there is equilibrium diminished by electrifying the liquid. given by (169) 8irA" ffV ' substituting the value of dald we have dt. 1212). dv therefore  = i 2 e da . show that e remains constant as the liquid evaporates. p. in other words that the vapour proceeding from the electrified liquid is not electrified. case and . Thus the new term .
p a small fraction.n plprtrir T. nlnrerl in Electricity also produces an is upon the vapour pressure when a. Effect of an electric field the drop fiplrl. so = 4 x 10 _7 . in sign to that due The effect of electrification is to diminish the vapour density when there is equilibrium between the liquid and the vapour. is about i'3 x 10".is unity.t1><=> .lating power of the air would break down and the value of e/a 2 electricity is escape. this value will be independent effect of the size of the Comparing equations (170) and (172) we see that drop. the maximum due to electrification is about equal in to a curvature magnitude though opposite of 1/4 of a centimetre. fall in thunderstorms. so that this effect We to should therefore be larger than an help to produce may the large drops of rain which 87. it therefore increases the tendency of the vapour to deposit on the liquid. expect an electrified drop of rain unelectrified one.pf not charged but merely us snnnnsp flint. upon the vapour effect pressure. the maximum alteration in the vapour density will be given by the equation now RQ that for water vapour P P at 10 C. The maximum air at the when the sphere surrounded by in electrostatic measure : atmospheric pressure is about 120 and as o.
calling this is large compared with p we have F and remembering that a so that the effect of electrification is on a neighbouring body state again to diminish the vapour density in the of . the potential energy due to the mutual action of the electrified point and the drop of water is _ 2Jf '(/'*')' so that the increase in the mean Lagrangian function is and therefore by (168) the change the vapour when Sp in in a state of equilibrium the density is of given by the equation Sp 7 __ ~ i cr i J3 \2 e 2 a2 2 R9 op ~K f r + e^a* \da (f' "?) f'(f*a we have ^s 2 Substituting for dajd^ from (169) p if <?: crp 2 __ ' J 4 1 i  "' be small compared with /then approximately 2 8p_ 3 i '~ i__ e Now /A/ 2 is the force at the centre of the drop due to the electrified point.from P. Vol. i. p. 232). Then (Maxwell's Electricity and Magnetism.
given by 22 x io . the potential energy possessed by the liquid in virtue of this strain is L2ll 2 k <r' so that and therefore by equation (168) Sp _ ~p~~ 2 or approximately j ^ <r i_ p / I" p for water /e 2/?$ ov so that the effect on the vapour pressure of the compression due to the pressure of icoo atmospheres is at the temperature of 15 C. then if k be the modulus of resistance to compression. Effect of strain upon vapour pressure. We shall now investigate upon the state of the vapour pressure depends Let us compression of the liquid. how suppose that the pressure p acts upon the liquid.88. In the next paragraph we shall consider another effect due to pressure which exceot for exceedingly laree pressures . = 10 Sp _ i for ether the effect would be given by = approximately.
is #W log where v is ' the volume of the vessel above the liquid. f]. If however that it we remember the air when above must expand and do work we a portion of the liquid evaporates shall see that this cannot be the case. of mass of each Then the mean Lagrangian function for the water vapour Let . water. We to investigate the magnitude of this increase and shall In the first case we shall suppose that consider two cases. It is generally believed that the equilibrium vapour pressure of water depends only upon the temperature of the water and not upon the pressure . be the masses of the vapour. iv l} a these substances respectively. and air the mean potential energy of unit w. that it is for example the vacuum as under atmospheric pressure. the air and liquid are placed in a closed vessel whose volume remains constant. it must by the principle of 84 go on further when air is present than in a vacuum. The mean Lagrangian equation (161) function for the water is by nyO + 17/1 (0)  tfw. respectively . w .same in a produced by an indifferent gas. so that the vapour density will be shall now go on increased by the presence of the air.accompanied by a diminution in the density of the air. and therefore by an increase in its mean Lagrangian function. and the mean Lagrangian function for the air is . but that since evaporation is .equilibrium vapour pressure. .
......' which is equal to/'/ " Hence we may write equation (176) as 1 p p or..... a or since or is very large compared with p. Sw l if Sp be the change in p due to the presence of the the corresponding change in w..Now air. + 2 =o . *** Now if ... ' p or av (176). ' . and be the compression due to the p the pressure due to the water vapour.. <'> S/ be the change in the pressure of the water vapour due to the presence of the air so that equation (177) becomes . so that w will be increased by the of the air will increase the pressure and l presence of the air.. soThe presence cause the liquid to be more compressed than it would be if the air were away...... .. we have by this equation s 8w.. S^ will be to this pressure due proportional to (/+/') &? and unless the the air amounts to many thousands of will atmospheres term be very small compared with 07.. If 8e pressure ff of the air.....
The other case we shall consider is when the pressure acting on the system remains constant. The only change We we shall shall have to make it in the mean Lagrangian fix function is to add to that of the system producing the steady external pressure. We may suppose in order to a quantity of mercury placed our ideas that this system is on the piston. then if the steady pressure per unit area the potential energy is equal to so that the P mean Lagrangian function of this system 7/V is . which may be be supposed to move vertically up and down. For ether the increase would be about one part in So that 220. for each atmosphere of pressure the vapour pressure of water is increased by about one part in twelve hundred.p so that equation (177) p" becomes ^. 90. use the same notation as before._e! > and thus the alteration in the a vapour pressure produced by an is external pressure of an atmosphere 8p given by the equation _ density of steam p I2OO atmospheric pressure density of water at = JL_ atoC.
We see from this result that (apart from any other cause) rain drops will form more easily when the barometer is low similar result to the it is than when high. . Sp p = P cr one we obtained before. be the change produced by the external pressure.y e(w /. Regnault's experiments seem to show that the vapour pressure in a vacuum is greater by nearly 5 per cent.gives log . m^=p cr or a.R6 dv dv Now .and />=/+/ i dv =f cr the above equation reduces to RQ log or if Sjo . Since .RQ +f(0) / (^) . than when there is air at atmospheric pressure above the liquid .and where / and /' are the pressures due to the water vapour and air respectively.) + = o.
LllUUgll. w 1 is the intrinsic potential energy of unit mass of the dissolved gas. The expression (178) is the quantity we denoted by x in is v and The only variable in x which involves dv'ld = i/o. so that we have 84.S V r o JZ'Oe p If 8p be the increase in the vapour pressure caused by the the pressure this gas would produce dissolved gas.LCUU. to nothing like the extent of 5 per cent... Effect its of absorbed air on the vapour liquid contains some gas diffused volume which remains behind when it evaporates. When the through (157) the mean value of its Lagrangian by function will diminish 84 the presence of the gas dissolved throughout the volume will diminish the equilibrium vapour pressure. CUJ..11 CVL1VJ11. LU pJ.UVt. then the Lagrangian as evaporation goes on.VJU... (178).. so that function of the gas is *ffO\Qg^K/+f(6) where . 91. v' the volume of the liquid in which it is dissolved.. do LUC following investigation will show. P . Thus by pressure.. the evaporation of the liquid will cause the volume occupied by the gas to diminish and its density to increase. Let e be the mass of the dissolved gas. CUCl*L 111 11113 U. d and therefore by (168) P= RQJL p v'<r _..
under the pressure of 760 millimetres of mercury were determined by Bunsen and are given P in the following table : Hydrogen Nitrogen Air 019 0203 0247 Carbonic Acid 179 Chlorine 3 0361 so that according to equation (180) the vapour pressure of water saturated with air will be lowered by about one part in 50. The volumes of the various gases which one volume of water will absorb at oC. and p the density of steam at the atmospheric pressure TT.000.V equation (179) may be written crp So that since p approximately is very small compared with <r we have S# f = cr P (180). equation (180) may be written And since p / a is about i / 1200 we see that " V p / z>\ 1200 where (P) is the pressure expressed in atmospheres. ^ ' or if/ be the vapour pressure. In this investigation we have assumed that the properties . when saturated with carbonic acid by about i part in 660 and when with chlorine by about i part in 400.
supposing salt remains behind when the liquid evaporates. p the density of its vapour at the atmospheric pressure. iv. Van t Untersuchungen. 92. The effect of dissolved salt . 1886) has pointed out that Pfeffer's pressure. and that the pressure salt in a dilute solution exert the would exert if exerted by these molecules obeys Boyle's and Gay Lussac's law. are not altered by that the the properties of the liquid the presence of the salt the results of the if Thus preceding section will apply. (P) the pressure in atmospheres which would be exerted by the dissolved salt is /*>. This being so. show that the molecules of a (Pfeffer. and we shall have. dissolved experiments on the in water osmotic pressure produced by Osmotische salts same pressure as they they were in the gaseous state at the same temperature and occupying a volume equal to that of the liquid in which the salt is dissolved. 401)._ . (" L'equilibre chimique dans les systemes gazeux ou dissous a l'e"tat dilue. p. 1877) and Raoult's experiments on the effect of on dissolved salts the freezing point of solutions (Annales de mc Chimie. Leip/ig. p. xx. f^) where o the density of the liquid.some case the diminution of the vapour pressure is greater than if of the gas were to be set free when the liquid evaporates. on the vapour Hoff. 6 serie. 239." Archives Neerlandais. the mean Lagrangian function for the salt dissolved in the liquid is the same as that of an equal mass of the salt in the gaseous state filling the volume occupied by the liquid.
the diminution in vapour pressure when one equivalent of the salt is dissolved in a kilogramme of the solvent. quantity of salt will by Avogadro's law produce the same pressure as 2 grammes of hydrogen per litre. the diminution in . then P/O. C 4 10 O. We see from equation (181) that the quantity of salt dissolved.is the density of the solvent.(molecular weight of is x 10 8 . Another way of expressing the same thing is that where Sfi when one equivalent of the salt is dissolved in zooo* equivalents of the solvent. C 2 0. where p/cr is about 1/380. i.. if it i were dissolved in alcohol. brevity a strength of one equivalent per . equivalent in grammes of the salt dissolved in a kilogrammeof the solvent. this H diminution in the vapour pressure is proportional to the We can also express the result of If is the pressure due to one equation as follows. H then the vapour pressure would be diminished by about part in 10. in TOOO m grammes where m is the molecular weight of the solvent. that is about 22 for atmospheres it .e. is the pressure in atmospheres due to one equi P valent of the salt dissolved in a litre of the solvent.) we may 8/> write equation (181) as solvent) x i  .This. Hence Bo P= tha t 2 5 /(density of hydrogen at atmospheric pressure. if this quantity of salt were dissolved in water would by equation (181) since p/cr is about 1/1200 diminish the vapour pressure by about i part in 55. the vapour pressure would be reduced by about one part in 17.litre. if it were dissolved in ether. where p/a. where o.is about 1/220.
. while p' the absolute temperature. Now of if s salt in unit be the strength of the solution. w In this case instead of equation (179) y we shall have / o \ (l82). be nearly independent varies very slowly with it. that the properties of the solvent were unaltered by the presence of the salt. Z) + S^+T? * t dw' y df] P +=0 <r .. then we must regard as a function of the quantity of salt dissolved. proportional to see that the ratio plp ought to of the temperature since <r only we In the preceding investigation we have assumed 93. and that all the solvent did was to enable the salt to exist in a condition in which the molecules were very far apart. is the change in w' produced by the presence of i.. the quantity dw' ' dw' s n ^^~ becomes ~dT' so that equation (182) p If the change in w' is proportional to the strength of the solution then ..e. p <rj where Sw' the salt.. is inversely. volume of the solvent. If however the properties of the solvent are altered by f the presence of the salt.and since P is directly.
while the we investigated in the preceding section Avas proportional to the first power. which agrees very well with the results we have just obtained. Raonlt.in the expression QW is cs . dixf s as the second. has recently found that when one equivalent of a substance is dissolved in 100 equivalents of a solvent the vapour pressure is reduced by i '05 parts in 100. so that the effect produced by the alteration of the properties of the solvent depends upon the squares effect and higher powers of the concentration. p. 1433. Compiles Rendiis 104. and therefore when the solution is dilute is relatively the more important. .
PROPERTIES OF DILUTE SOLUTIONS. 2. 3. In this case we have four substances that to consider. and will H not by the Hamiltonian principle alter the value when the system is in equilibrium. solvent in THE effect produced on the vapour pressure of any by dissolving other substances in it has been discussed the last chapter in this chapter we shall consider some 94. . Let us suppose we have a closed cylinder containing a gas and a liquid and that we wish to find how much of the gas will be absorbed by the liquid. The gas dissolved in the liquid. Absorption of gases by liquids. The vapour of the liquid.CHAPTER XII. 1. variation The which of which we shall suppose to take place. is that correto the sponding escape of a small quantity of gas from the . other properties possessed by dilute solutions. The liquid. 4. The free gas.
is The last term when the amount of gas absorbed not large will be very nearly independent of the quantity of gas dissolved.R9 log (.. and v' the volume of the liquid or that occupied by the dissolved gas. + /' (0) ~ &v' ( I 85). z/ is the volume occupied by the free gas. then by the Hamiltonian principle stationary when w H the system is in equilibrium.}= Equation (186) may be written (186). t. If we gas which correspond to denote the sum of the expressions (183).for the free gas R6 for the dissolved gas log r + f (0} w ( 1 84). . so that if we suppose a small variation to be caused by a quantity of gas 8 escaping from the liquid then we must have for equilibrium this is equivalent to R6 log .RQ +/(0) wJRB log + 1 Vp / / + RO /' (6) + ' ^{^ + V (0)>F'. (184) and (185) by is H. and where w' and f'(0) are the quantities for the dissolved where and/(0) for the free gas.
unit provided the solutions are dilute. can be exnlained bv the same nrincinles. we see from this equation that pip is constant. Chemie. Thus either the properties of the free gas can not be quite the same as those of the dissolved gas. The diffusion of salts through the solvent. a solid or gas which can dissolve in two fluids which do not mix. p. is.{/' /'(&)} + j+ r {rryO s /(0)  ifW. that the quantity of gas in unit volume of the liquid is This is Henry's proportional to the density of the free gas. which goes on until the solution acquires a definite state. We can prove in this way that when there is equilibrium when the fluids are shaken up together then. In the following . experiments showed that the value of the ratio p'/P depends upon the temperature. or else p'/p would be the same at all the properties of the water are altered by the gas dissolved in it. (see Ostwald's Lehrbuch der allgemeinen.where free is c is a constant and p and p are the densities of the and dissolved gas respectively. hence we see from equation (187) that w f (6) . A similar investigation will apply to the case of 95. law of the absorption of gases by liquids and it has been Bunsen's verified by the researches of Bunsen and others. Since the temperature constant. a process 96. the amount dissolved in volume of one fluid will bear a constant ratio to that dissolved in the same volume of the other i. 401).} cannot be zero. otherwise temperatures.
Let the two vessels be filled height h with water containing a certain quantity of salt dissolved in it. the lower vessel may be salt. then 77 of salt goes from the there is if change must not If the is alter the salt value of J? } equilibrium the mean in Lagrangian function of the vessels. rnnrlihnn . the potential be the height of the lower vessel energy of the salt in taken to be gh'. so that there is  g/i' in the expression for the mean Lagrangian term fjg(/i function of this similarly there is the + //) in the expression for the salt dissolved in the mean Lagrangian function of the vessel. then we wish to find how the salt is divided between the vessels when equilibrium salt if // is established. Let and 17 be the quantities of respectively.shallow vessel whose volume is v' situated at a above the lower vessel. then in the lower and upper vessels above some the term fixed plane. and solvent the two solutions are dilute the only part of H which varies nnrl 1hp the sum of the expressions (188) and (189). upper Thus using the same notation for the as before the expression mean Lagrangian is function of the salt dissolved in the lower vessel og the mean Lagrangian function of the salt dissolved in the upper vessel is lower to this Let us suppose that a quantity the upper vessel.
. we shall therefore investigate an expression it for this effect by comparing and see what information can be gained with the results of the abovementioned is experiments.. (190). 165. xxxi. A large on the bilitat effect number of experiments have been made of dissolved salts on the coefficients of com" pressibility of various solutions (see Schumann Compressivon Chlorid Losungen.or if '.... 7)' are the masses of salt in unit volume in the lower and upper vessels respectively or = e RQ .. 14. p. 2 v) i.. p... Ann... and that k' is its coefficient of compressi bility. 1886).. v}.. 97.." Wied. .. xxix. is So that the concentration of the solution when there equilibrium varies in the same way with the height as the density of a gas under the action of gravity.. us suppose that the solution whose original volume v is subjected to a hydrostatic pressure p which reduces its volume to v... . 1887 and Rontgen and Schneider. Then the mean Lagrangian function of the solution is and the system producing the pressure i (v. + ^. Wied. (v .. Let.. N 2k V.. Ann..
. .. S? is 1 ing diminution in volume by (191) given by the equation IRQ zr gt s . // ^ r i fa.... Let us see what the magnitude of this effect would be in if the pressure of the molecules were the only way which .. If p be increased by Sfi. H by rfv.. J f> \ . va *+ = ' or or since i> is very nearly equal to v equation in the form we may write this So that the apparent coefficient of compressibility is K i+7#' J thus the pressure due to the molecules of the dissolved salt produces a decrease in the coefficient of compressibility. the correspondP.where If is the mass of the is salt. then since If Let us suppose that the volume is stationary we must have is increased dH _ ~ dv or T7 n ' k is V '/ + ^ * V = o .. now RQjv let us call this the pressure due to the molecules of the salt. .. sum of these expressions then by the Hamiltonian principle PI must be stationary when there is the equilibrium. (191)...
and hence we conclude that in addition The following will paper to producing a pressure in the solvent the dissolved salt must directly alter its elastic properties. P pressibility is very nearly equal to or to one part in i/Pk'. table taken from Rontgen's and Schneider's show that the effect of dissolved salts is sometimes more than a hundredfold that calculated on the above assumptions. one equivalent per strength of the reduction in the to coefficient of compressibility 2'2 X 10 ought to one part in X 2'2 X IO that is to one part in 1000.litre 2 2 of water. solution is we see that litre when the amount IU . is 22 atmospheres or in absolute measure x io 7 Since the reduction in the coefficient of com. .
Mr Adie. By following his directions I have succeeded in making such membranes though the number of failures was very large compared with the number of successes. the work required to lift the water being supplied by the expansion of the molecules of the dissolved salt. A diaphragm Avhich it said to be impervious to all salts allows water to pass through it can be made by allowing weak solutions of sulphate of copper and ferrocyanide of potassium to diffuse into a porous plate from opposite though sides. who is making some investigations on this subject at the Cavendish Laboratory. finds that the membranes are formed more readily if ferric chloride is used instead of copper sulphate. The molecules of the salt may be regarded as confined within a limited volume by the solvent. Leipzig. 1877. when they meet form a membrane Detailed instructions for making these membranes are given in Pfeffer's Osmotischc Untersuchungen. This constitutes the wellknown phenomenon is of osmosis. then if the vessel is placed in water with its top above the surface water will flow up into the vessel through the bottom. height to which the fluid will rise in the Let us suppose that the osmometer is a long . if the solution was contained in a vessel provided with a they will take bottom pervious to water but impervious to the substance dissolved in it.solutions. We shall now attempt to find by means of Hamilton's principle the osmometer. and any opportunity of expanding even though Thus they may have to do work to enable them to do so. these solutions of the kind desired.
... (192)... and for the liquid outside the y + / (<9)K+ 1 : 7) ..... using the same notation as hitherto. the is 877 sum flows of (192).....the tube occupied by the solution... Then..+&) .. where z is the height of the centre of gravity of the molecules above some fixed plane. equili Then since if there is no contraction dz ' dv drj dt] where a is the area of the cross section of the osmometer. the mean Lagrangian function for the salt is log ?b + t/(e)t (*>.. (194). (193) and (194)..... the height of the centre of gravity of the water outside the osmometer the quantities for the liquid inside the tube are denoted by affixing dashes to the symbols where y is denoting the corresponding quantities for the water outside the tube.. (193). salt The mean Lagrangian is function for the liquid in the tube nyO + y/SWviW+g*) tube ( .. Let us suppose that a quantity of water into the osmometer. By the Hamiltonian principle the value of If. and . is stationary when there brium.
lent per Si litre. the strength of the solution in the osmometer is one equiva1 where/ salt. p is + ^/i is about 660 about 22 atmospheres. Archiv A7f~/"i'l'n"i') /I /7'}V t 7'>r^ . If the liquid is in a constant volume we can not allowed to expand but confined easily prove in a similar way if the properties of the solvent are not changed by the addition of the salt then when there is equilibrium the pressure exerted by the fluid in the osmometer must be that the same as is that due to t' the molecules of the salt. so that in this case feet. This result given by jn Van n Hoff {Uequilibre chiniiqne.___ AH f\ leads to the equation if the properties of the solution are not altered by the presalt sence of the then and equation (195) becomes is the pressure due to the molecules of the dissolved and h the height of a column of water whose mass is If the same as that of the salt dissolved in the osmometer. that is the water would flow into the osmometer until the height of the liquid in the tube is nearly an eighth of a mile above the level of the water outside.
8 . and KN0 . a rise in the osmometer if the increase in the mean Lagran gian function of the liquid inside the osmometer caused by the addition of unit mass of water is greater than the diminution in the outside the Anvfhincr mean Lagrangian function in the water osmometer caused by the abstraction of unit flint mass of water. it would still follow from the Hamiltonian principle that there would be salt and that of potassium nitrate 3 . for it enables us to find the number of molecules in a given mass of the gas.. for potassium nitrate it is the molecule KNO We upon see as in 90 that the terms in (195) depending the alteration of the properties of the solvent by the addition of the salt do not contain any powers of the strength of the solution below the second. me pressure calculated on the above principles for potassium sulphate is 97 centimetres if we assume that the molecule is K a SO. measurement of the osmotic pressure produced by any on the above assumptions give the same information about the structure of the molecule of the salt salt solution will A in the solution as a vapour density determination does about the structure of the gas whose vapour density is determined. and 194 167 if if the molecule is is \ (K 2 SOJ.nuraie mai aue to 1704 cenumeires. Thus Pfeffer's measurement of the os motic pressure due to potassium sulphate suggests that the relation between the composition of the molecule of this K 8 SO 4 is represented by and not by K 8 SO 4 and KN0 3 Even if we do not assume that the molecules of a salt produce a pressure analogous to that of a gas. PJIUQPC n rOiancyp nf tlnm Irinrl will .
T. Surface Tension of Solutions. The experi ments of Rontgen and Schneider already alluded to have proved that for most solutions the product of the height to which the solution rises in a capillary tube into the density of the solution water. then if is the mass of water in the of the rest of the water. and is greater for a solution of a salt than for pure that for dilute solutions of most (though not all) substances this product increases with the strength of the It follows from this that the tension of the surface solution. 99. of contact of the solution with air increases with the strength of the solution. that To investigate the magnitude of this effect let us suppose we have a thin film whose area is S and surface tension thread. On this account the indications of the osmometer are somewhat ambiguous. and before coining to any definite conclusion as to the structure of the molecule of the salt to use several solvents it would be necessary and to show that the osmotic height varied as the absolute temperature. e that the rest of the liquid. the mean Lagrangian . while the tension of the surface of contact of the solution with glass or any other solid body diminishes as the solution gets stronger. 17 that in film. connected with the bulk of the liquid by a capillary Let be the mass of salt in the thin film.will rise in which no heat was evolved higher in the osmometer than one oi similar strength in dilution. The solution variation of the surface tension with the strength of may cause the strength of the solution to vary near the surface.
cw L 3 Let us suppose that a mass of the change in the salt 8 mean Lagrangian goes into the film. function is and p. e f 7fei P where / is is the thickness of the film. function for the rest of the liquid The mean Lagrangian is V nRB log p<> + ij/(0) . thus if we film in contact with a solid there would be more salt . this by the Hamiltonian principle must vanish. the surface tension of a solution in contact with a solid dihad a minished as the strength of the solution increased.TJW^ + ty6 + /. while if the surface tension is diminished by the additension tion of salt there will be more salt in unit volume of the film We saw that than in unit volume of the rest of the liquid.wuuic v ib me vuiuizie ui me mm. Thus if the surface increased by the addition of the salt there will be less salt per unit volume in the film than in the liquid in bulk. we get ' P = jL^ RO<tt P or if T' is the increase in the surface tension when the mass of salt in unit volume is increased by unity 1 1T' > P_.(0) . thus if p are the masses of salt in unit volume of the film and liquid respectively.
so that the more quickly moving fluid at the centre would get weaker and weaker. could be given . if a piece of trickling through finely divided silica.Ur. flow through a capillary tube the salt would have a tendency to flow to the sides. when it flows through finely divided . unless the salt has a very strong affinity for the water the solution after rising some height in the filter paper becomes colourless. again. Many experiis mental illustrations of this one of these an experiment tried by Dr Monckman and myself at the Cavendish Laboratory. and such a solution strength will increase in silica. If a small quantity of paraffin oil be mixed with water the surface tension of the solution against a solid is greater than that of water. in which a deep coloured solution of potassium permanganate emerged almost colourless after Again. it such a solution were to stronger man the rest. filter paper be dipped into a coloured solution of a salt such as potassium permanganate.
i. the molecules in the one condition being in dissociation more complex than those in the other.nto the atoms I and I . as in the case of O 4 splits up into nitrogen tetroxide. between portions of matter in two different states. NO or . while on the other hand some of the . so we have also equilibrium between portions of the same substance in two different conditions. both in the gaseous state. This phenomenon has some analogy with that of as in the latter case we have equilibrium evaporation two molecules of 2 . dissociating" as it is called into the simpler ones. 100. and matter being able to pass from one condition into the other by the more " complex molecules splitting up. matter being able to pass from the one state to the other by evaporation and condensation. THE Hamiltonian method can be used for the pur pose of obtaining the laws which govern the phenomena of dissociation. such as the iodine molecule I 2 i. the gaseous and the liquid.CHAPTER XIII. where the molecule 2 N when the molecule of chloride of ammonium splits up into ammonia and hydrochloric acid. or of a complex molecule into simpler ones. DISSOCIATION. the splitting up of a molecule into its atoms.e.
and for the simpler gas p^R^Q. where v is (196).Let us first investigate the case when . the density of the simpler gas will at the same pressure and temperature be half that of the complex gas and therefore *. is The mean Lagrangian function of the complex gas ^0 log 3p +/. Since the molecules of the complex gas consist of two of those of the simpler gas. The mean Lagrangian iJR m function for the simpler gas is 01og& + iiS. contained and the volume of the vessel in which the gas is the potential energy of unit mass of the l w complex gas. = **.(*) to. Let us suppose that the system is contained in a closed is the mass of the vessel and that complex molecules.P*. 17 that of the simpler ones. We shall for the present assume that both gases obey Boyle's law and that the fundamental equation for the complex gas is /> = *.. (197). p the density and the absolute temperature. as in iodine.(ff)iiw. the more complex systems are diatomic molecules and the simpler ones atoms. the complex molecules contain two of the simpler ones this is the case when. . as well as in such cases as the dissociation of N 2 4 . where p is the pressure.
me presence 01 me otner. principle the value (196) and (197). = o and the condition dH ^r is ' equivalent to JRJ log ZKJlJ+f... 77 or v.R 2 B log ^ = o . we must have the simpler molecules combining to form is stationary Then since the value of H dH Since the mass of the gas 5 *r a is constant + ST. us suppose that the state of equilibrium is disturbed by H a mass S of complex ones. of is Let stationary when the system is in equilibrium.. In experiments on dissociation quantity usually . is me sum 01 me expressions By the Hamiltonian.. (6) w.. or since we have ** 6 10g This can be written where < (0) is a function of but not of the . (198)..
& _ __*. The pressure in the vessel . is The density of the gas at this pressure ' g+7] v so that ' A the density at the pressure TT is given b. = ( j /7 = H we have ^ = 15"Z /w Z)A " rf : . ' the density D of the complex gas at this pressure is by the equation D = R~V so that > . equation A j + V JL ..^j +277 and therefore +277 ~ D ^ ' and since > 7 .the same pressure. is ae f\R  _L _! v or since v z ' R = zR^ 2 77 f* I the pressure equals Rfi.
Ann. We shall now investigate the difference produced in the state of equilibrium of a dissociable ons if it and the com nor puts into which it is decoirmosed . 337). and a. the way in Before discussing this equation we shall investigate which it must be modified if the gas does not obey Boyle's law. the value of p\pB for a perfect gas of the same and b and a constants depending upon the nature of the gas. Van the two. /c are small constants depending upon 3 the nature of the gas. der Waals formula. Clausius' formula is R9 K where R is the same as in Van der Waals formula for the same gas. p. which is 3 is rather the simpler of JRO a where jR is specific gravity.where 1 01. gases have been given by Formulae connecting the pressure and volume in such Van der Waals (Die Continuitdt dcs gasformigen unafliissigen Zustandes) and Clausius (Wied. ix. /3.
and where jR a as before. the density of the complex gas . with a cc for the Lagrangian fund The condition dH *T will now lead to the equation log ( I  bj) + log /:  +. we have the term where p is spending term in the expression of the simpler gas./: f^ ^rw. . = 2R lt Then we can easily prove that instead of the term W?log^ P in the mean Lagrangian function.
so that b and 2 are so small that their squares may be neglected. +1  log . the pressure and the temperature may be different although equation (202) shows that the relation between the masses of the dissociated and undissociated gases is the same.. QvRfl is approximately equal to p // are both small fractions while /= IO H if and a and p the pressure is one l 2 atmosphere.... we may write this equation as if l Now 2 _2((lil> 1 }i. equation (202) may be written as an equation of the same form as when the gases obeyed The connexion between the masses of the Boyle's law. complex and simple gases and the vapour density of the mixture will not however be the same as when the gases obeyed Boyle's law. l v/ v v ~W IV a we suppose that the deviations from Boyle's Law are slight.. and so the relation between the vapour density.. It would be an interesting problem vapour density of the mixture to find an expression for the in terms of the masses . (202).2(ai zl> 2 )ri (wiW2 ) e A'rf L=<f since (0) c vR* ..
They found that so long as the temperature remains constant the vapour density of nitrogen tetroxide at different pressures is . p. Ann. p. discusses the results of experiments on the vapour densities of these substances at different temperatures and pressures and has found that they agree fairly well with the results calculated by formula (203). formic acid. p. xxn. According to Boltzmann and this agrees with (200) if <j6 : (0) is proportional to 6. acetic acid and perchloride of his Gibbs in paper (" On phosphorus. Quite recently however E. 1884). 277/1879). p. xvm. and L. 306). xxvn. 102. Formulae corresponding to equation (200) deduced from thermodynamical considerations have been given by Willard Gibbs (Equilibrium of Heterogeneous Substances. 239) and Boltzmann (Wied." American Journal of Science and Art. Ami. 39. Natanson have made a most elaborate investigation of the vapour density of nitrogen tetroxide at various temperatures and pressures (Wied.doubt assumed. Thus according to Gibbs this agrees with (200) if <^ (&) is constant. the vapour densities of peroxide of nitrogen.
number . using the same notation as the when time is the 99. 1884. number number of and therefore the shorter the time the Since the results of a large complex molecule lasts. these conditions lead to the equation and only if. considered the question of dissociation from the point of view of the kinetic theory of gases. (0) different from that adopted by either Gibbs or Bolt/mann would probably fit in better with the observations. This will evidently not be the case if the breaking up of the complex of molecules the greater the molecules this is due to their collision with other molecules. is independent of the number of molecules of the gas in unit volume. and that the gas attains a steady state broken up in in the unit It is in that time. 103. for in case the greater the collisions. without splitting up into simpler ones. The differences seem however to be too great to be explained altogether in this way. number of complex molecules same as the number formed shown that. and a value of c. In the Philosophical Magazine for October. supposing that the I complex molecules are continually being broken up while the simpler ones are continually combining. Part of this difference may arise because the N 2 O 4 does not obey Boyle's law.in it is constant. the average time a complex molecule lasts if. is greater than can be accounted for by errors of experiment.
Hence we conclude that when we have a gas some of whose molecules are complex and keep breaking up into simpler molecules which after a time recombine to form the complex if the splitting up of the complex moledue to their striking against other molecules. that is dissociation will go ation goes on on further than it did in the undisturbed state. the pressure due to the gas will not be the sum of the pressures which the dissociated and undissociated gases would produce if each were by itself in the vessel. then if the Lagrangian function from some external cause is increased by x we see by equation (198) that SX the change in X is given by the equation Thus if x increases as diminishes that is as dissoci SX will be positive. dissociation If we denote fflv^ by X and use X as a measure of the amount of dissociation. This is another illustration of the general principle stated in 84 that any slight alteration in the conditions under which a system is placed which increases the rate of increase of the . then cules is 104.cal principles which hold whenever the two gases obey Avogadro's law and whenever the pressure produced by a mixture of gases is the sum of the pressures which would be produced by each of the gases separately if the other were removed. We shall now consider how external influences in may modify the amount of at some given gas which takes place a given temperature and pressure. molecules.
since there is perfect from the liquid to the gaseous state. we should continuity tion. the result of which as the is expressed by the relation the term ajv* is due to the action of the surface tension of the gas (Van der Waals. 34). things as surface other gases. Though much more difficult to detect the existence of the action of surface tension experimentally in gases than in liquids there is still some evidence of its existence from experiments such as those of Bosscha on the forms clouds of fog and tobacco smoke. Though expect that the outer layer of molecules of a gas which was not in the "perfect" condition would like the outer layer in a liquid be under different conditions from the other molecules. undfliissigcn Die Continuitat ties gasformigen Zwtands. corresponding to those analogous case of evaporation. we considered the presence of in the Effect of surface tension upon dissocia the effects of surface tension are not nearly so prominent in gases as in liquids. it is p. and would therefore not possess the same amount of energy same number of molecules in the midst of the gas.We shall now consider the effects on dissociation of such tension. 105. electrification. of There must therefore be a term in the expression for the . In Van der Waals' theory of the relation between the pressure and volume in an imperfect gas. still.
so that by (205) o ... x 3'24 x T= ' io 4 "V . to form a rough estimate of the magnitude of energy of unit area of surface of gas According to Van der Waals the is measured by xa &' where x a distance comparable with molecular distances.TS. and 3 under atmospheric pressure a[v is a pressure of about is 324 x If io~" 4 we take the molecular 4 atmospheres. . Now for a cubic centimetre of ether vapour at oC. (206). in which case dTld is positive.X in me .. the dissociation will be greater the larger the surface of the gas. or in absolute measure 3^24 x io 7 distance x as io~ we have . is . m xa. Thus.. for in most cases the dissociated gas approaches more nearly than the other to the state of a perfect gas thus in most cases dTld will be positive. g 104. = TO _..... now endeavour this effect. if the surface tension diminishes as dissociation goes on..Lagrangian junction. so that dissociation will be facilitated : by increasing the surface of the Let us gas... We should expect a priori that the surface tension of the dissociated gas would be smaller than that of the undissociated.
\ In order to form a rough estimate of the value of let us suppose that the complex gas possesses surface tension but that the simpler one approach than for to the truth. as the value of is does not. we have . T. at which we reckoned and substituting for T its value.. then Since the surface tension varies as a/v to the square of the density. v the volume in Let p be the density of the complex which it is contained. so that i 2 . gas. it is proportional T dl~ and thus dT _ ~ z_ ? dp_ ~dl dT ~ _ 2T dg so that vp' 2 we have SA ST v (207. this is an a and therefore of the surface tension very much greater for complex gases simple ones.A RBc. A Rflp Now at the atmospheric pressure.
say if /=io~ that if ."X" i* 10 ' the thickness of the film were comparable with so 7 then the surface molecular dimension. such as spongy platinum The value of given above is only part of the or charcoal. such films occur adhering to glass fibres or to matter in a fine state of division. and T A B is due to the energy of thin layers their junction differing by a finite and B next amount from the energy of A possessed by equally thin layers in their interior. surface tension of the surface of contact of the gas and the The surface tension of the surfaces separating solid. depend upon the substance and thus the nature of the walls of vessels used for chemical experiments may affect the chemical combination which goes on inside them. T may to which the film adheres. The value of 1 06. Van 't Hoff has described some experiments which seem to show . Thus the value of the surface tension effects due may be much greater than that given above and the to it may therefore be greater than our estimate. In the preceding investigation we have calculated the part of the energy of the layer of one own molecules. of these substances arising from the effects produced by its in addition to this there is the energy arising as the energy from the action of the glass on the gas as well in the thin film of glass. This example may be sufficient to show that if we have the gas in thin films surface tension may produce a very considerable effect . The abnormal energy of these layers is due to the want of symmetry of the action on the two sides. tension would produce very large effects.
107. small. the effect of electrification on dissociation must be very and we shall not stop to determine it. is no electric discharge electrification will not produce any ciation goes on. unless the specific inductive capacity of the gas changes as dissoAs all the specific inductive capacities of gases which have been determined are very nearly equal. where we have thin of gas. the effects observed might be explained by considerations of this kind. it is doubtful whether they can be due films to the effect of surface tension. also found that when the walls of the vessel were covered with a deposit of cyamelide the rate of polymerization of Victor Meyer too cyanic acid was increased threefold.tne area oi the walls was increased six times. me rate of He polymerization was increased in the ratio of 4 to 3. but it is probable that in the case of many catalytic actions. . If the properties of the 108. Effect of a neutral gas. When the effects produced are of this magnitude. The presence of a the maximum amount of dissociation. effect upon the final state of the system. found that the decomposition of carbonic acid takes place in a porcelain vessel at a temperature several hundred degrees lower than in a platinum vessel. neutral gas are not affected in any way by the presence of the gas which is dissociating. When there Effect of Electricity upon Dissociation. the value of the mean Lagrangian function of the neutral gas will not change as dissociation The presence of this gas will therefore not affect goes on.
If the dissociation were at all catalytic. and the only way or reconciling the two is to suppose that the gas is not perfectly neutral but has its properties affected to some extent by the presence of the other gases.to the result we nave just arrived at. and C1 2 .(*)  . 109. and C1 2 respectively. In the preceding investigations we have assumed splits up into two molecules or In some cases however the constituents into which the molecule splits up are different. as a typical case. Let us take the dissociation of phosphorus pentachloride and let be the masses of PC1 6 PC1 3 rj. that the complex molecule atoms of the same kind. as for example when PC16 splits up into PCI. . . We can easily modify the preceding investigation to suit cases of this kind.. we might explain the action of the neutral gas by supposing that by itself forming a film on the surface of the vessel it prevented to some extent the dissociating gas from doing so. . Then the mean Lagrangian functions for these gases are respectively log +</.
rtfy....where ^. then we have and the equation foo to find/ (^ is + '. is (208). remembering that ^ fi . ( 2 9)' where ^ is a function of the temperature. rj.. fj discuss the effect upon of alterations in the values of and to Differentiating (209) we get..!*) + ^) = ^ (^o^) p . we see that the condition dH leads to the equation ^_^ and thus 17^' constant. We shall now v. . is constant as long as the temperature ation Let us suppose that the values of before dissocicommenced were and that the mass c^p of i) Q . and C1 2 respectively. hence. PCI. ^=^=^3. gets decomposed... writing y for . are the alterations in the masses of PCl PCI. .
Then the mean T. 3 have only to slightly modify the preceding work to be the mass applicable to this case. though the results of the dissociation are in the gaseous state. Is positive. tends to stop the dissociation. 2 the gaseous. In this case. for as soon as the molecule PC1 S breaks up the free .npinn . so that the presence of free PCl^ and Cl. as in the former.a0ra. cules of PCL d 51 and scop the dissociation. the body which dissociates is in the solid or liquid state instead of. so that dissociation be promoted by increasing the volume is in which a given (211) and (212) quantity of gas we see that both dp\d^ and dp\d^n are negative. as in the previous instances. Let as before rj and those of the components of the dissociating body.av dp_ <fy v __ ~~ dp We will see from (210) that dpjdv confined. In some cases.. theory indicates that in this way if there is no catalytic action the presence of a neutral gas would not produce any effect. The dissociation of NH S 5 into H S and NH We make it is an example of this kind. :! chlorine will be surrounded by such a multitude of molethat most of it will recombine and form PCL. From equations Wurtz proved experimentally that there was very little dissociation of PC1 5 when it was placed in an atmosphere of We can also see from general principles that this must PC1 be so. into which it is dissociated.
the density of the solid or liquid ^= A ^i f i? is ((^ iff) \ / + C a)lVlC. In this case the dissociation would be affected to a small extent by the presence of a neutral gas. the neutral gas above it expands. dissociation hindered by the presence in excess of either of the results of the dissociation.J) log   " and Then from the condition dH <*r' we get.2W 2 C 1V 3 ) + 3 e &'*~ ( 2+ 3) U (1\ V . since d dv (dt\ + </). Hence we see by neutral gas will (84) that the presence of the . for if the system is confined in a closed vessel the volume of the solid or liquid diminishes as it evaporates. \ _ . and its Lagrangian function therefore increases. It follows from this equation that. as before. dn cs and c are the combining weights of the gases into a which the solid dissociates. i and where . and o.
c its <r the density of the solid or liquid. combining Since e/z/o the ratio of the mass of the gas to the mass of the same volume of the dissociable solid. seen Dissociation of Salts in Solution.easily show that if K denotes the value of yyv and . where a. is extremely small. OK the change produced by the presence of the neutral S/< gas. to we see that for a pressure of 100 atmospheres SK = K 3 approximately. We have 92 that Van 't Hoff has given reasons for believing that the molecules of a salt in a dilute solution exert the same pressure as they would if they were in the gaseous state at the same temperature and volume and that the : mean Lagrangian is function of the molecules in the solution as that of the therefore the same same number of gaseous might therefore expect from analogy that in some cases these molecules would be dissociated though the effects of this dissociation might not be so recognisable molecules.is about 15. unless its pressure amounts some hundreds of atmospheres. as in the case of gases. We Many cases of the dissociation . If we take the case of salammoniac. no. so that if the pressure were increased by about 3*3 atmo spheres the change in K would be about one per cent. then _ fa + c e } K V<T where is e is weight and the mass of the neutral gas. we see that the effect produced by the neutral gas.
still it produced by the of the solvent The salt may change the properties and the effects attributed to the dissociation may in reality be due to this change.ent interpretation.. The 97 proves that this must be so in some cases. Now though we may salt does produce the effects that would be this hypothetical distribution of gaseous moledoes not follow that these are the only effects salt. . salt solutions In the case of the dissociation of ties the proper of the solution might alter as the dissociation progressed. This reasoning is founded on tine assumption that all the effects due to the dissolved salt may be completely explained merely by supposing the volume occupied by the solvent to be filled with the molecules of admit that the the salt in the gaseous condition. The supporters effect of this theory urge that for the salt to it produce the which in some cases necessary to suppose that the molecules of the if they salt exert a greater pressure than they would occupied the same volume at the same temperature when in does. for we saw that the effects of the addition of salt on the of the molecules investigation in compressibility of the solution were much too large to be explained by any amount of dissociation. Thus the dissociation might alter the surface tension of the which case the amount of dissociation would depend upon the shape and volume of the solution or it might alter the coefficient of compressibility or the volume solution. it is the gaseous condition. in . produced by cules.
We cases of the next investigation.of the dissolved salt would probably be much more sus ceptible to external physical influences than the dissociation shall however discuss these as particular of a gas. which deals with a much more general case of chemical equilibrium between either gases or dilute solutions. .
the mean mass of each of these substances. sodium sulphate. be the masses of the substances A. sulphuric acid and sodium the nitrate: nitric acid acts on the sodium sulphate and which the four substances A. in. . 3 . the when there is equilibrium. The problem we have quantity of each to discuss is to find. GENERAL CASE OF CHEMICAL EQUILIBRIUM. the case are respectively nitric acid. C. C. B. while the sulphuric acid acts on the sodium nitrate and forms sodium sulphate and nitric acid. Let unit . w v w w w s. w potential energy of the mean potential . B. while C by its action on D produces is A A in wellknown example of this kind of action C. B. THE case we shall consider in this chapter is the equilibrium of four substances A. such that proby its action on A B duces C and >. f]. D forms sodium nitrate and sulphuric acid. e D respectively. either gases or in dilute solutions. D. when any quantities of four such substances are mixed together.CHAPTER XIV.
B. C. The above expressions represent the mean Lagrangian functions equally well whether the substances A. for the properties of this may alter as chemical combination goes on. J3. Then the mean Lagrangian v *i C and D are respectively where v is the volume in which the substances are confined. Z> are gases or dilute solutions. w 6 then mean Lagrangian the potential energy of unit mass. function will be of the form . provided the solutions are sodilute that the molecules of the substances dissolved in them exercise the same the same temperature in If we mean Lagrangian function of the solvent. are considering solutions we shall require the the mass of the its solvent.that of B C p p that of and that of D f functions of A. If TT is pressure as they would if placed at the same volume when empty.
C. J3. Thus. c= are d= 2. while c of C and d of have appeared. in the case of the mixture of sulphuric and nitric acids. Let 8 2.. then a 2. D represent the relative densities of A.. respectively.. number de. 83 84 . then 8j..chemical action which goes on between the four substances be represented by . sodium sulphate. sodium nitrate and sodium sulphate. then the alterations in the of molecules of A. D are respectively proportional to . Na s N a . JB..... From equation disappear it (2 14) we see that if a molecules of A must be because they have combined with b of JB to produce c of C and d of D. sulphuric acid and sodium nitrate in the solution are represented respectively by HNO i. a :i . D are altered by d. C. Na S0 2 4) H S0 2 4 . J3... since the equation which expresses the reaction is 2HNO if a + Na S0 B 4 H SO 2 4 + aNaNO. Na a S0 4 H SO 4 and NaNO . so that I) molecules of B have also disappeared.. at the same temperatures and pressures. d. (213). If however the molecules of these substances represented by H^NgO.. then a=b=c=d= it is i. l>~i. dy. Thus we see that necessary to know the structure of the molecule as well as its relative composition. 3.. D If the masses of A. C.. the molecules of nitric acid.
Ytet J elll. C. ^ " Let us take then since first the case H when A. so that if we suppose the equilibrium displaced by the quantity dt of A the change in combining with the proper quantity of the Hamiltonian function must be zero.p log .So that dt] de Now when the system is in equilibrium the value of the Hamiltonian function must be stationary. D are gases..aS^d + 6 log   log ^ m= <7f) 4 nil I 4. hence we must B have dH =Q dt i (2I6) J3. function is the sum of the mean Lagrangian for these substances the condition (216) with the help of equations (215) gives the equation ^O log Vp . .
(219) <l> i (Q)vc+d6t!w so that the equations of equilibrium for gases solutions are of exactly the same form.. . } ^^ tf+dab V =6(0) clttf ft Xj (218) ' V where equals Q is the mean Lagrangian function of the solvent and The value of dQjd^ will be zero if the properties of the solvent do not change as chemical action goes on j in any case since the solutions are very dilute the properties of the solvent may be assumed to be changed by an amount probe a portional to the quantity.of salt dissolved. the potential energy diminishes as creases. dQld will not involve ... Q will therefore e and linear function of . Now D form A the potential energy... and in this case as in the former one & <. any of these we have quantities... or e.d In the case of dilute solutions the equation correis easily seen to be a_ ' dw _ a... sponding to (217) yc.= yc d d ft . 112. dQ ft . 77.. 113.. and when the quantity of heat is large its mechanical equivalent may be taken as a measure of the decrease in by to unity.when <($) is a function of & but does not involve .. rj. and dilute The potential energy of the system value of dwjd^ measures the increase in the when the mass of is increased combine if heat is produced when C and inand J3.
then a=2. that is. and equaLet . the combination of Cand one of these substances gives out. According to Berthelot's law of "Maximum Work" the reaction accompanied by the formation of heat goes on as far as possible at all temperatures. =  i i x io'. law To ordinary temperatures. dw ^ = 143x10 1S .or either or c D will go on until must vanish. oxygen and water respectively. b=i. d=o. gramme of hydrogen with oxygen 34000 calories are given out. tion (218) becomes dm If we J? 1 5 substitute for/(0) <p (0) its value given shall find that in this case = in C/0' oC. in other words the reaction attended by the production of heat will at the zero of absolute temperature go on as far as possible. where the combination is represented by the equation 2 at temperatures as be practically true at illustrate this let us take all will H 2 H0 2 =2H 2 0. any combination at Berthelot's high as 1000 all C. rj. and since on page 270 we For hydrogen at the combination of one J 5 ' . =2. the equation (218) however shows that this is strictly true only at the zero of temperature. be the quantities of hydrogen. For substances Which give out large quantities of heat when they combine equation (218) shows that if there is that the com bination increases so rapidly as the temperature diminishes. the case of hydrogen and oxygen. Let us suppose that equivalent quantities of hydrogen ..
The We effect of pressure on chemical equi9) have by equation (2 T thus if c rf a^rb e the ratio /'V is independent of the volume.s in the VPRSP! HOPS not rhnncrp the reaction pries on. librium. Since the a molecules chemical reaction is such that when acts on A . =So that at this x io~ 5 . of A and b of B disappear while if c of C and d of D are produced. we see that a + b = c+d the number of molen. Thus in a case like this is very considerable dissociation at one temperature tion at compatible with almost complete combinaa temperature not very much lower. . 114. one half of the equivalents combine.x that at _L_ xijr " (ixf~&** Suppose 1092 C. then the value of x at 546 C. is given by the equation thus approximately i #  e 3 . temperature only about one in five hundred thousand of the molecules will be left uncombined. so that will mix given quantities of the four substances the if we amount of chemical action which will go on be independent of the volume into which the substances are put.
volume + b is greater than c+d then the f e the smaller will be the ratio of to rf Now the action of C on Z> tends to diminish this ratio. . and that the effect of increasing the volume is to favour that reaction which in the is accompanied by an increase In other words. D . taking for the sake of simplicity b = c= d= i. when they have reached the state of equilibrium a quantity S. while that of greater than A on B the tends to increase and is if a+ b is c+d number of molecules increased when C acts on D and diminished when A acts on B. 115. that Let us suppose that the masses of the four substances before combination begins are e and r. . S ji\ a dw . larger the "17*. C. pressure. while that action which produces an increase in volume is hindered by which produces a diminution is helped it. Let us now consider a more closely some of the results of equation (219). If a v. . the case when a A. by This is another example of the law stated in little (84). ./ of A has disappeared. then by equations (215) we have and equation (219) becomes / ? .stances are placed. Thus we see from equation (219) that when chemical combination alters the number of molecules the state of equilibrium depends upon the volume within which the substances are confined.\ / . it. B. S j. the chemical number of molecules.
the quantities e . . Se respectively. y remaining constant. p when is increased by let . when Then we 17.. p. then we may put And equation (220) becomes if we put  k .substances were taken. The is effects due to what are called "mass actions. e 8/ 2 8^ a are increased ." that present the effects produced initially substances by varying the quantities of the four may be deduced at once from this equation. and A be t the respective increases . . then tp Thus we may write equa and is called the affinity coefficient of the reaction (Muir's Principles of Chemistry. by S?7 8^ . tion (220) in the form ( } where k is constant as long as the temperature remains unchanged. Let S/j be the increase in rj . get at once from equation (221) .. 417).
where y is the positive quantity or r + f\ + t + e . we may easily prove that *.%. . In the more general case. and further that the effects of equal small changes in the masses of A. so that any increase positive while S^a /S . C and 8pJ8rj are see from these equations that tyJ8 8/4 /8e a^e negative. C. where a. B. b. We in the quantity of A and . c? d are not each put equal to unity.Z? initially present increases the amount of combination stances. while initially any that goes on between these subincrease in the quantities of and C D present decreases the amount of combination. before combination takes place are inversely D proportional to the amount of these substances present in the state of equilibrium.
xm). A The number of collisions in unit time is propor numbers of molecules of and B. it always explaining we have just cited. + _* C mass of ^ which has disappeared. 1 1 6. It would seem however that the principles from which Guldberg and Waage deduced their equations would when a. as given in the works true. b. C. B. c and d are not all equal lead to equation (219) rather than (221). case when a = b = c = di. and so is proportional to The number of cases in which combination takes place may be taken therefore to be k&) when k is a quantity which is independent of the tional to the product of the 77. According to their theory. the A. Modernen Theoricn der Chewic. and Lothar Meyer. chemical combination between A and B will take place. The case when a = b = c=d\s the only one however in which the expression deduced from Hamilton's principle agrees with that given by Guldberg and Waage.. then in a certain proportion of the collisions which occur between the molecules of and B. The expression (221) agrees with the formula obtained by Guldberg and Waage from quite different principles (see Muir's Principles of Chemistry. 407. ? 1} <*8 3 + 4. A quantities of number In other words.ab] V where here aSj/ is . .l + 8. y= the 8. chap. p. the equation (221) is while according to the theory we have been is only true when a = b = c = d. for their Consider first the point of view seems to be as follows. states and enter of molecules which leave the A* D B . present.
If on the other hand the equation which represents the chemiwhich is cal reaction is * (A) + (Ji) = (C) + 2 (2>). the then chemical combination will A number of such combinations will be proportional to and not to 7]g. and again between one of C and one of D. We can easily see however that the above reasoning is only applicable when chemical combination takes place between one molecule of A and one of J3. and thus the number of molecules of A which disappear owing to their combination with B molecules may be represented by krjg* similarly the number of .. which agrees with equation (zig) but not with Guldberg and Waage's equation. take place when one molecule of J3 is in collision with two of simultaneously. or in other words when a b c = d=i. there is some ambiguity as to what the molecule of the dissolved salt or acid really is. 117. ^ molecules of the D which disappear and of A which appear combination of C and D may be represented by by 2 7i/< and since in the state of equilibrium the number of molecules of A which disappear must be the same as the number which appear we must have ^=w.as the number or molecules number which or A and J3 formed must be the same disappear. For example.k'k Guld berg's and Waage's equation. take the case already mentioned . and therefore kfr=. As we noticed before in (107).
. . 2 and not by NaNO. . instead of 85 and 63 to produce the effects observed in solutions of one gramme equivalent per litre. nitric acid and sodium sulphate respectively... This reaction has been investigated by Thomsen (Thermo2 Na2 N 0. 121) and in the following table 2. e/fj e are the masses of the sulphuric acid.CHEMICAL COMBINATION. it would be necessary to dissolve 170 and 126 grammes of these substances in a litre of water. the lowering of the vapour pressure of the . is constant provided the temperature remains unaltered. N HNO H . then Naa S0 4 iH 2 S0 4 (or by 3> 3) constant as long as the temperature is unaltered. . p. nitrate. sodium where 97. solution and the effect of the salt or acid point. cheinische Untersuchungen i. HNO. If the 4 H S0 2 and NaNo 3 molecules are represented by then by equation (219) <rYi? s HNO a.07 . H . We can however use the formula (219) giving the amount of chemical action between these substances to decide this point. NaN0 is .j 22/ or by Na s 2 O a or whether the represented by NaNO molecule of nitric acid is represented by or N2 8 3 This point could probably be settled by experiments on osmotic pressure. if however the molecules are represented by N 2 O Na 2 SO 4 S S0 4 and H .. If the molecules are represented )3 upon N"a the freezing 8 fi by NO HN . Na SO a 4. HNO .
. N Pfeffer's determination (98) of th< . It will be seen from this table that when there only a nitric acid present initially.to the number of cnermcni equivalents ot nitric acid Deiore is combination commences. HN . becaus weak solutions a very small error in the determine in tions will produce a considerable error this the value c cF/tf or ctffr If there was any change of kind in the constitutio of the molecules as the strength of the solution increase it would probably show itself in the effect of the substanc on the osmotic pressure. solvent produced by the addition of the . and c the lowering of the freezing point. in very dilute solutions the molecules of nitric 'acid anc sodium possibly be represented by HNO. or else that the molecule: 2 G 2 presented by of sulphuric acid and sodium sulphate are represented b] nitrate may . (219) seems to agree but that it ceases to be any approximation when the solution now equation (221) agrees bettei gets stronger. formula very small quantity of with the observations as well as (221)... NaNO 3 but that in stronger solutions either they are reNa 2 a O. W ments with in the dilute solutions as to those with strong.H SO 4 JNa a S0 4 osmotic pressure produced by a potassium sulphate solutioi suggests that the molecule is represented by  (K 2 SO 4 ).. and that From this we should conclude thai with the experiments. even though these effec were complicated by the alteration in the properties of tl salt. on the vapour pressure. ought not however to attach as much weight to the exper: .
(222 If two of the ).. As an example of a case where the conditions more complicated than in those discussed in the last paragraph. we shall consider a case investigated by Horstmann Watts' Dictionary of Chetnistiy.. barium carbonate.. as for example when C potassium carbonate. We see from these equations that the amount of com bination which goes on does not depend on the masses of the insoluble substances. is A D easily prove that (223) . for the case Avhen only one of the substances example when the four bodies are oxalic acid. calcium chloride.. hydrochloric acid. 3rd Supple119... then we can potassium sulphate. substances are insoluble solids.... J3 barium sulphate.insoluble one. The mean Lagrangian form function for D will now be of the and the condition dH = * will lead to the equation '* .. and calcium oxalate.. are rather ( . Let us take first D is an insoluble solid.
P = R$K with a corresponding notation for the others. e. Let the mean Lagrangian function for the hydrogen be where v ti\ is mean potential energy of unit mass The mean Lagrangian function of the other the the volume in which the gases are confined.. c. and of hydrogen.. c& . .. T i+=a constant i cz i : A c. and the absolute temperature for carbonic acid 9 be for hydrogen pXJp. Now whatever changes go on among the various gases we have since the quantity of hydrogen is constant i = c i a constant : ^ since the carbon is constant 7] 7T += ^ c * a constant : since the oxygen i is constant "n it ' + + c. TT.. these are three equations between five unknown quantities. . gases will be given by analogous expressions. and be their molecular weights. the density p. let c^ be the masses of these substances respectively.. Let the relation between the pressure p.
constant \ <*T! 7~ /) =0 constant " Remembering l that a R c = && = Rj: l = & = R f.. Chemical Combination of Gases already referred we divide (224) by (225) we get fw \ .. ! the first equation gives Jj i ^ 3 = i (0) e^'i 9 ^'V constant .... so that must have (dH\ \~jt~) \ " ! (dH\ ( 6 /r..i ta\ i la w} l* ' l en c6...and when is constant When function the system is in equilibrium the all mean Lagrangi is stationary for possible variations....... w is the mean potential energy of the mixture These are of the same form as the equations from kinematical considerations alone in If I obtain t my paper on to..... ( 2 ^ ( and the second i i_ /^'\ ^ constnnt . f<hv\ . U^VjrU ? . where gases. (225).. (v) ..
.acid always bears a constant ratio to the ratio of quantity of free hydrogen to that of free carbonic ox: This was the result obtained by Horstmann in the exp ments before mentioned.
known the amount of chemical combination can be . and denote chemical action between of 77 in the state by k. for it is convenient to have a name for it it. determined.CHAPTER XV. The more intense the and J3 the smaller the values of equilibrium and therefore the larger it A the value of We have by equation (220) _ /& <t_ dQ ' a iho = </>. we shall therefore call the coefficient of chemical combination A . and since when it independent of the values of 17. . SINCE the value of S? IV is is e. The alterations which we suppose to take place . and B k. (e}e~W^ e'W shall ~% (226). 120. EFFECTS PRODUCED BY ALTERATIONS IN THE PHYSICAL CONDITIONS ON THE COEFFICIENT OF CHEMICAL COMBINATION.
Effect of Surface Tension. . ' . ' (227) If the substances with to deal are gases we must put Q and 8Q equal to we were discussing dissociation changes state of We considered when in chapter xiv. chemical equilibrium in will and the apply to the more general problem we We see from (227) that any cause are discussing now. due The first effect we shall consider is that to the surface tension of the solution.&& J = a l ~j? 6~d d^Q + a dfau ~R$~d which we have zero. most of the results in the physical conditions which could influence the this case. We know the strength and the composition changes as chemical action goes on the surface tension of the solvent and therefore its mean that the surface tension depends upon the nature of the solution. so that since Lagrangian function will change. 121. and therefore by the principle we have just stated the conditions for equilibrium will be altered by the surface tension. . producing a change in the potential energy which increases obtained then any chemical action goes on will tend to stop this action which will not have to go on so far before attaining equilibrium as it would if the disturbing cause had been absent as and vice versd. We shall now go on solutions to consider more particularly the cases of dilute and the effects produced upon chemical equilibrium by changes in the properties of the solvent arising from the progress of chemical change.
d 2'2 X 10 " L _ when the quantity increased by one grammeequivalent. we have. then since . If c is the molecular weight of the substance whose mass is . much 3 as 5 or 6 so that of the order ^H A . xxix.coefficient equation (227) the effect of the surface tension on the of chemical combination is given by the equation d( 5^~ ^L A T\ >' k Rf'd^ Let us endeavour to get some idea of the magnitude of this effect. . Ann. if for simplicity T a be put equal to unity. as . then where T' is the increase in ^when the quantity is increased Now the experiments by one grammeequivalent per litre. 165) show that T' even in the case of simple salts 8& r is may be r . of Rontgen and Schneider (" Oberflachen Spannung von Fliissigkeiten. If v be the volume of the vessel whose surface we shall is Nowrt/ (AT~)/d the solution the increase in AT in is suppose to remain constant as combination goes on." Wied.at o"C.
This of say about io~ . then at the top of the . Thus film the chemical action in a space such as a thin throughout which the forces producing capillary phenomena of it are active might be very different from the chemical action in the same substance in bulk when most would be free from the action of such forces. chloroform is slowly deposited as a white precipitate. If the surface tension increases as the chemical action tend to stop the action. Thus in very thin films the influence of capillarity might be sufficient to modify completely the nature of chemical equilibrium. then S/&//6 might be as large as 6.is k of the order . while if the surface tension diminishes as the action goes on. One that called by its discoverer Liebreich " the dead space in chemical reactions. This point does not seem to 'have received as much attention as it deserves. but there are some phenomena which seem to point to the existence of such an of these is effect. though we should not expect goes on the it to do much in the body of a fluid. If the proportion of alkali to chloral is properly adjusted." which is well illustrated by the behaviour of an alkaline solution of chloral hydrate. io 7 t : thus if the thickness of the film is is i/ioooo of a centimetre the value of k 7 If the altered by about '6 per cent thickness of the layer is comparable with molecular distance. and if this solution is placed in a testtube. the capillarity will capillarity will tend to increase the action.5. course implies that the conditions of equilibrium would be completely altered.
no deposit seems to be formed. the effect of pressure in this case is proportional to the amount of the pressure: the second 122. some experiments in the Cavendish Laboratory on the changes in the surface tension of the solution as the reaction went on.This In fine capillary tubes too. for in this case the surface tension would increase as chemical action went on. Soc. vi. and would Dr Monckman made therefore tend to stop this action. 66). The first is when the volume of the liquid under pressure alters as chemical action goes on. Effects duce effects of effect is when the coefficient of compressibility of the liquid changes as the chemical action goes on. and he found that it increased to a very considerable extent. the effect of pressure due to this cause is proportional to the square of . phenomenon could be explained on the above if principles increases the surface tension of the alkaline solution when is the alkali combines with the chloral and chloroform deposited. Liveing in his paper " of Capillary Action in some Chemical Decompositions (Proceedings Camb. itself would increase the thickness of the dead effects Some other produced by surface tension are " On the Influence discussed by Prof. The thickness of the dead space (from i to 2 mm. due to pressure. Pressure can protwo kinds upon chemical action. in Liebreich's experiments) is somewhat greater than we should have expected. Phil. p. so that this case is in accordance with our theory. but any want of uniformity in the liquid such as that produced by the deposition of chloroform space.
Let us now endeavour to form some estimate of t probable size of this effect. Thus y cubic centimetres per gramme A formed we have by (228) k k if the pressure is x atmospher cxya 4 2'2 X IO ' The cases in which in general y will have the great value are those in which we have some of the bodies solution while others are precipitated. if we suppose tl when a salt is dissolved the volume of the solvent is altered then v will in eener.il r. and we have by equation (227) 8/t a d . If the molecules of t substance produce the same pressure as if they were the gaseous state.mpnil . in other woi .luncuon is Pv. the value of C'V'/t'V increased if than they would be there and therefore f and 17 were no external pressu Thus is the external pressure tends to stop that action whi accompanied by an increase in volume. and vice versd. then at oC. hp nni. 8/ is positive. where c is the volume increases by the combining weight of the substance. dv Thus less if # increases with is .
so that it would require a pressure of 22o/ac atmospheres to change the coefficient of combination by one per cent. Let us now consider the effect on the chemical equilibrium when the coefficient of compressibility changes as the chemical action goes on. and therefore in the expression for the mean Lagrangian function the term \v'a"K.6 KV = P.dx k 2R. Let <r be the expansion or contraction of the solution. v its volume. K its bulkmodulus. change in the coefficient of combination due to the change in K as the chemical action progresses we have If 8% be the by equation (227) S ~ a 7//T . the reaction will be sensitive to the influence of pressure. then in the expression for is the potential energy of the solvent there the term W*. . thus if the substances taking part in the reaction have large combining weights. d Now if P be the external pressure a Substituting for get the value given ai>' by this equation we k _ = ~k P' dK 'K* ^Rfi dk""'' let is some idea of the magnitude of this effect suppose that when the mass of A in the solution get To us in .
Thus when a solution of copper sulphate is placed on an iron plate plate copper' is deposited and iron dissolved. while a pressure of 1000 atmospheres would it by io per cent. so that in this case.where c is the molecular weight of Ik . K NOW and for water. y = ax*y ~io' . and if this be placed over the poles of a powerful electromagnet . CR$=2"2 K 1U . The magnetic properties of solutions are generally so feeble that we cannot expect magnetism to produce any effect In some of the except upon those which contain iron. to retard the chemical action by Effect of magnetism on chemical action. 123. k approximately. we have therefore hy equation (229) __ ay / P_ ^ TO X I0 10 . supposing a unity. chemical actions however in which iron is dissolved or deposited magnetism does seem to affect the result. = 2'2 X I0 is So that if the pressure 8/1 x atmospheres . the effect of a pressure of 100 atmospheres would be to alter k by alter i/io per cent. ' ri From ments given the results of Rontgen and Schneider's experiin (97) we see that y will often be as large as i/io. If the bulkmodulus increases as is increases then the action of the pressure which increases.
. then if k' and k" are constant there is by 34 the term  1  (T \ 2 77 v + 177 k {k I' 2 V + HIv + H'I'v' ) 1 in the expression for the mean Lagrangian (227) function. /' that forces and K and solution and iron these substances. which agrees with the results of experiment. can show in a similar way that any chemical action which produces an increase in the coefficient of magnetization is We hindered by the action of magnetic forces. and H' the magnetic k" the coefficients of magnetization of the plate respectively."be the intensity of magnetization of the of the iron plate. v and if the volumes of H solution. Thus we have by equation ~ __ k zR v a where cr is the density of the iron. Since H= H' = k'l. and the quantity of iron in the solution. hence .since k = ^"/^Vj the quantity of iron dissolved will be least where 7' is greatest. that is where the magnetic field is strongest. K'l'. we get k zR^ is Since in practice 7'7/^'cr .see that greater than 72 & dk' v\K we Ik will be positive and will increase with 7'.
p7r the coefficient of magnetization of the solution.. Then if of the salt in unit volume of the first and second of these vessels respectively. r dk' Iog n.To cause calculate the let magnitude of the effect due to this us suppose that the solution is contained in two vessels connected with each other by a tube of small bore r and that one vessel is force vanishes. the coefficient of magnetization increases with the strength of the solution the magnetic force will tend to drive Thus if the salt from the weak to the strong parts of the magnetic field. the variation of the in the we can easily prove by equating to zero mean Lagrangian function for the liquid i two vessels that ^ where k' is . . the other in one where placed in a region where the magnetic it is constant and and 17 are the number of molecules equal to H.
and endeavour to find how the amount of salt dissolved depends upon various physical circumstances. 17 that of the solution. by a/. THE in been those cases we have hitherto considered have which gases and dilute solutions have been in this chapter chiefly concerned. Then the mean Lagrangian function for the salt is . Let us consider the case of a mixture of salt and solvent in equilibrium. fusion and solidification in which and solids play the chief part. LIQUID. Let masses of the salt and solution respectively. we shall consider the phenomena liquids of solution. Solution.CHAPTER XVI. CHANGE OF STATE FROM SOLID TO 124. Let Let us be the mass of the for brevity salt. 125. salt denote Tlp/dO for unit volume of the by w and the corresponding quantity for the solution ws be the potential energies of unit /..
If v be the volume of the salt and we put then the Lagrangian function for the salt may be written 000 + / (0)  &e/. p that of the solution. and 71' is the volume of the solution.J /.. f We and w^ do not depend upon the values of and 17 yet the values of O'. if <r be the density of the f a f \6 .T] > \ a . the Hamiltonian principle the value of the mean Lagrangian function of the salt and solution when in By equilibrium is stationary. ' ' (0) N ' /m + w l a +9 n p + a d v d. are the when disturbed the system is in equilibrium by a mass S of the salt then change in the value of salt. is The mean Lagrangian function for the solution with a similar notation where is the part of the kinetic energy of unit mass of a (0} the liquid which does not depend upon the controllable comust ordinates. that Let us suppose the conditions melting. H is. o/a and f do a (&) may so as the properties of the solution may and generally do alter that though remember O when the amount of salt the solution contains is altered.nates.
just as in the case of chemical combination. the other on the change produced in the coefficient of compressibility.. the effect due to the change in We may suppose that the external pressure is produced by a weight placed on a piston which presses on the fluid. effect of this kind we shall consider that of pressure and. we knew amount the amount But though the this how the quantities in this equation varied with of salt dissolved we could use it to determine of salt dissolved when the solution is saturated. pressure will produce two effects. .a' M if UiXJ i . where in this V\s.ve not this 'knowledge and therefore can not use in a given solvent. the increase when diminishes by S . a 9 Z7  w . equation to determine the solubility of a salt we can still get a good deal of informa tion from it about the effect produced by various physical circumstances on the solubility.. d . 126. the mean Lagrangian function of this system is pv. is The first . first Let us consider volume. we ha. one depending on the change of volume which takes place on solution. the volume of the salt is and solution .
/(0)/0 and a (0)/0 with the tem / perature. approxir corresponding change 8g in by equation mately given by the equation this equation is only approximate as we have neglected the variations of O. we have by equation (231) so that the change 8^ in the temperature which would produce the same effect as the pressure/ is given by the equation dw . If 8^ be the change produced by the pressure /. We shall endeavour to find the change in temperature which would produce the same effect on the solubility as the pressure/.dw. \d_ fiQ\\J^_l_ftQ\_*. then is. O'. We may regard }' the expression . dOf .( if dwz as a function of say/(). 6 be increased by 80 the (230). the temperature remaining constant.
while the volume increases as the salt dissolves the effect of will pressure be the same as that of a diminution in temperature. agrees with the results of equation (233). the column of which gives the name of the second the increase in volume when 100 salt c. mis will De measured by q the mechanical equivalent of the heat absorbed in this process at zero temperature. if the specific heat of the system does not change as the salt dissolves: making this substitution equation (232) becomes If the is is volume diminishes as the salt dissolves dV\d% positive.and ferro He found that when the volume cyanides of potassium.energy vvnen unit mass 01 me salt dissolves. The sodium chloride. The table results of his experiments are given in the following first the dissolved. 538. Society xn. 1863). or at any temperature. copper sulphate.c. the third the increase in the is salt dissolved when a pressure of 100 atmospheres ap . p. while when the volume This the solubility was increased by the same means. of the salt crystallizes out. so that if if q be positive the effect of pressure the same as that of an increase in temperature. The salts effect of pressure upon the solubility of various has been investigated by Sorby (Proceedings Royal >. increased on solution the solubility was diminished by diminished on solution pressure. salts he examined were and the ferri.
o C. p.x 41 x 58 10* (Ostwald's Lehrbuch der Allgemeinen Chemie.rotassium r erncyanide Potassium Sulphate 251 '335 28 4'4 3121 89 2914 2845 Potassium Ferrocyanide required to calculate by the aid of (233) the theoretical amount of the alteration in the solubility are given below. = 2r (Watts' Dictionary of Chemistry. 1819) the increase in solubility for each is degree centigrade . Specific gravity v. we shall always therefore take the heat of dissolution for the lowest temperature at which it has been observed. 170). Phy 310. The numbers The heat absorbed when the salt dissolves depends upon the strength of the solution and the temperature. p. xi. 335> et de According to GayLussac (Annales de Chemie sique. n. p. the value of q required for our purpose is that which corresponds to a saturated solution at the zero of absolute temperature. as due the variations in the value of q with temperature are probably to changes in the specific heat the effect of these will be smaller the lower the temperature. for a strong solution = ^=. is rapid this can only be a Sodium q at chloride. though when changes the variation with temperature very rough approximation.
As an example of the way in which the effects of presin is sure can be calculated from these data let us take the case of sodium chloride: since 1357/100 is the increase volume when i c. 311. 17% (Watts' Dictionary of Chemistry. 247). Increase of i C. salt XL p. v. Specific gravity = 26 (Watts' Dictionary '. (Ostwald. q at i5C. p. 1819). .c.Specific gravity ). Specific ii. 162). n. Ferricyanide of Potassium. = 127% (Watts' Dictionary. =2 2 (Watts' Dictionary of Chemistry.?= ~t 251 x 4! x 109 Lehrbuch. Increase of i salt C. .35 2 ) n. 247). = dissolved for a rise in temperature of v. P. Increase of salt dissolved for a rise in temperature of i C. Lehrluch. Annales de Chemie et de Physique.?= s x 41 x io (Ostwald. = dissolved for a rise in temperature of 2/ (GayLussac. 607). and 2*1 the specific gravity of the salt. of the salt crystallizes out. n. I have not been able to find corresponding data for the ferrocyanide of potassium. 591). = gravity i'8 (Watts' Dictionary of Chemistry. Potassium sulphate. v. ?at i5C.
then in the the term mean Lagrangian function of two there is where as before v and solution respectively. . legitimately modulus of the is and that of solvent k'. (B) = . 2 88.\w f. (9}\ .ke*v 2 z/ / 2 YV. is it necessary to inve when salt may k. flx ~ f. salt are the e volumes of the e' and and and their contractions.  . solubility is increased by the pressure by 56 parts in zoc Considering the imperfect nature of the data at solubility increases 'i3/ i disposal the agreement between the theory and the expi merits seems as close as could have been expected. x 1357 x 10 n = 44 C.iSC.\ d . If the bulk neglected the effect of the differei salt and the solution.+ . /mi [ . i . this . it '. so that by equation (233) of = 288 x 58 89 X 10 5'6 X 4'I X 2'I /=io 0= 8 . Taking term into account we find that the condit dH leads to the equation Of O rfQ' +_# . So far we have between the compressibility of the as this may be very considerable gate this effect in order to see omitted. and since the f r eac ^ degree.
may change as the takes place in the volume surface in contact with the glass or the the salt dissolves or the salt is secondly. Then in the expression for the solvent there is the term mean Lagrangian function of the 3TS. and again when deposited the surface of contact of when the salt is preand solution may change . let ^ be a surface of the solvent. cipitated as a fine powder this increase in surface may be very considerable. as in the cases examined by Sorby. 2 a 2 '\1 v'} \ . the alteration which may change the area of the air.T q \f Since /' is dl. Effect of Surface Tension affect upon the amount of Solubility. salt Surface tension may the required to saturate a solution in several ways. 2 k o10 . and in this case the effect of the pressure will be proportional to the square of the pressure and not to its first power. In the first place the surface tension of the solution salt dissolves. For very much larger pressures however the terms depending upon p" will be the most important. T its surface tension. of its original volume the terms s involving p are not so important as those involving f if the pressure is not more than 100 atmospheres. To find the effect of these changes on the solubility. 127. . 'J of the order io we see that if the change amounts which takes place in the volume of the salt when it dissolves to one per cent.
34).at] cr V v "  ' [_ar) J W. fluid is in Let us take as an example the case when the spherical drops and consider the effect of the change in volume which takes place as the salt dissolves.  IV. so that surface if TS increases will as the salt dissolves the effect of the it tension be to retard solution. then so that if S be the surface dS ' Q da 21 and therefore by equation (234) fiT . If a is the radius of the drop and i the increase in volume when unit mass of the salt dissolves. + r\ . 6 ~6 126 we see that the increase 80 in the proceeding as in temperature which Avould produce the same effect as the surface tension is given by the equation (. while if will increase the solubility TS diminishes.
then and if T' be the surface tension of the salt and solution we shall have !? = _3. we have ^ = ^7.:T. zT a i'8 x io' UJ at the temperature of 27 C. 8 i I  80 o a approximately. 10 solubility increases by 2 / for each degree of temperature the solubility of spray of this fineness would be diminished by about In this case if '6 / . ' 6 era q fc: in whirli 1'hf salt is rlpiinsitp. is very the salt were deposited from its solution as a very fine powder the effect of the increase in the surface might be much more considerable.80 V since J'is about 81.fi nrp . but Let us suppose that the salt is deposited in the shape of small spheres of radius a. the effect of the surface tension small. 1 1 ' so that if the radius of the drops was i/ioooo of a milli metre 86= and since the 2.
deposition of the so that surface tension would be much more efficacious in preventing deposition salt to dissolve. p. for this substance we have therefore. xxix. now consider the effect due to the alteration in the surface tension of the solution with the quantity of salt have as before dissolved. . If the salt before solution was not in a very finely divided condition the diminution in the surface caused by the solution would be much less than the increase in the surface due to the salt.we should have with these numbers for potassium sulphate 86 r = i . it than in helping the from the solution would thus tend to promote something analogous Let us to supersaturation. 209. approximately. approximately. This the solubility would be changed by about effect would help the salt to dissolve and prevent its deposition from the solution. We According to Rontgen and Schneider (Wied. Aunalen. dT ._ ~d 8l x 3 toT' : where v is the volume of solution substituting this value for . so that at zfC. 60 per cent. 1886) the surface tension of an 8 / solution of potassium sulphate is about 3 / greater than that of pure water.
then since we know by the laws of diffusion of gases through these substances that the diameter of the pores must be comparable with the mean free path of a molecule of the gas we may assume that a is of the order io~. Under this head we shall consider the influence . in a cylindrical tube of radius a. 128. the value W would be about is  i2C.= If the solution is approximately. If we suppose that these cylindrical tubes are of the dimensions of the pores in such substances as meerschaum or graphite. Liquefaction. S/z> = z/a. X1 J 10 if the angle of contact vanishes the increase in the surface tension of the surface The sign is changed because separating the solution and air in that separating the solution is and the equal to the diminution walls of the tube. which in the case of potassium sulphate an increase in the solubility by nearly 25 7 the surface tension of the air increases equivalent to In most cases from surface separating a solution with the amount of salt in it. In this case ?? ~6 = JL ~ 100 of ' so that at 27 C. so that in liquid in capillary spaces the salt will be more soluble than in liquid in bulk. and therefore 80 TJ 6 = 4 a approximately.
states. we may put where v If T] I is the volume of the solid. solid. the Lagrangian function of the liquid is is where Q.substances in different will not. of the substance in the solid Since the Lagrangian function proportional to the volume. the properties of the liquid change as the solid melts. the mass of the liquid. v' its volume.(0). Let be the mass of the is by 81 its mean Lagran gian function _ energy of unit mass is where iv l is the potential state. o/8 the potential energy of unit mass./ g (0) function which do not depend upon strain &c. expect that so long as the temperature remains constant these terms We would not alter much however the arrangement . They are and depend merely upon therefore independent of the arrangement of the molecules the number of the molecules and should therefore the kinetic energy possessed by each. they do not involve the controllable coordinates. as in that case.' is defined by the equation The terms are the parts of the Lagrangian /. } that is.
LIQUEFACTION. < Let us now consider the effect of a slight change in the physical conditions. so that in this case we We may regard the lefthand side of this equation as a function of 0. This change must vanish by the Hamiltonian principle when have the system is in equilibrium. If there is 257 no external pressure the change in the mean Lagrangian function of the solid and liquid when the mass 8 of the liquid freezes is  y) where o +/. effect of pressure upon the freezing If the external pressure is / then . (0) /. If this change increases the Lagrangian function by x and does not affect appreciably the values of Q/cr. which when equated to zero gives the temperature at which melting takes place. say (0). we have if the melting point is now 6 + 80. WKsolid and p are the densities of the and liquid respectively. fi'/p. or since </> (0) = o Let us consider the point.
if raised..But from equation (116) we have v constant and if of ice...i/cr. This is 84. hence whence if 80 be the increase in 6 caused by the pressure^ . is if negative or the melting point is the body contracts on solidification is positive and the melting point is raised by pressure. James Thomson and verified by the experiments of Sir William This ... the wellknown effect predicted by Prof... the latent heat of liquefaction and Sv = i/p .. the Lagrangian function increases when the liquid the temperature at which freezing takes place is in other words freezing is facilitated. the heat supplied is just sufficient to melt unit mass 8Q = X. if another example of the principle of We see from equation (238) that the body expands on 89 solidification SO is lowered by pressure. <238>. comparing this with (237) we (6) see that d$ _ \ d6 and equation (237) becomes So that freezes.
the potential energy due to the strain in the solid and / liquid 2 is V 3:so ft ] + \v j> +P (v + v'\ that in the is mean Lagrangian the term (i function of the solid and liquid there P where 8 K (!) + < 8' . k' that of the liquid.also be proportional to the square of the pressure. let k be the modulus of compression Let of the solid. <r free from pressure. and volumes. this effect in the case of ice Let us find the magnitude of The only constant is of elasticity for ice which Young's modulus.K*8"> ' .. the freezing point will be altered to the square of the pressure.and water.8')} . are the compressions and z> and z and p the densities of the solid and liquid the when If 86 be the rise in the melting point due to this cause we see from (239) that _?!'_ I Po 2 ^ "o i /fe'8"\ 2 Po / So that unless /ecr = k'p by an amount proportional . which Sevan de10 the termined by flexure experiments to be about 6 x i modulus of compression k is therefore not likely to be less has been determined .i vj . as before / be the pressure per unit area acting on the solid and liquid. 17 2 .
and the Lagrangian function therefore increase as the ice melts. while for pressure we have just been investigatinj If k<r is greater than k'p then this effect ii the larger. is in the opposite direction to that' which is proportional tc the first power of the pressure. Let us suppose that we have a cylindrical bar of ice twistec with a uniform twist about its axis it will possess energ) in virtue of the strain. This acts in the same direction as the effect due the alteration in t volume on solidification. Effect of torsion upon the freezing point . effect of pressure upon reversed whei 129. Comparing thi expression with equation (238) we see that for pressures les than about 9000 atmospheres the effect depending on th' change in volume is is greater than this the effect the more important. the outside) the water will be free from and will noi therefore possess any energy corresponding to that possessed by the twisted ice. Let us take the case of a thin cylindrical tube of ice. so that in these cases tin is the freezing point the pressure exceeds a critical value. that is.roughly. We can easily calculate the magnitude of this effect. it will freezing point. but if it melts (suppose on strain. so that will facilitate by the principle stated in 84 the torsion lower the the melting of the ice. the case of substances which contract when they solidif. Thus the potential energy will diminish. since .
So that W be the rise in the freezing point produced by the torsion we have i d = ^ 4 {*< +^ we have since a and b are If the sides melt equally approximately equal 4 <+*)<> so that S _ = _!!f!^! 20A (?~~" since To get some estimate of the magnitude of this effect let us suppose that the cylinder is i centimetre in radius. and .then in the the terms mean Lagrangian function of the tube there are where v is the volume of the if ice.
separation of the water and air if the ice rises to the surface of the drop.. Thus when a portion of a salt gether. The effect of dissolved salt on the freezing point. solution freezes. tude of the this effect. to balance this however we have two fresh surfaces formed where the ice meets the water and air. the formation of the other would tend to promote two would tend to pre vent ice not know the surface tension between it.jr = 400 6 approximately. let be the mass of the is salt. J L * so that 86 = 68 C. the particles of salt are brought closer toand work has therefore to be done upon them. So that in this case the ice on the surface would melt unless the temperature was lower than 130. the Lagrangian function therefore diminishes. Effect of surface tension on the freezing If a portion of a drop of water freezes.  68 C. 131. but as we do and water and between ice and air we cannot calculate which of these tendencies would have the upper hand. the formation of the ice will cause a diminution in the surface of point. and we see by equation (239) that the presence of the salt will tend toTo calculate the magniprevent the water from freezing. the mean Lagrangian function is for the salt if the solution dilute . and the ice from such a solution is identical with that from pure water. then using same notation as before. When a salt solution freezes the salt appears toremain behind. the diminution in the first surface freezing.
. or in absolute 7 = 273. in. Thus equation (239) becomes w where 8 (O'//o) i r + 0d due of to are the changes in Q'//o and/2 (0) and 8f a (6) the salt. froze at rg . v. chiefly organic salts. et Annaks de Chimie found that solutions of this de Physique. but that the freezing . p. = r8C. then 2 sr is measure about p is 2 x io 7 about 22 atmospheres.quantity wnicn cnanges in ishes me expression is v wmcn cnmin by &/p. if we consider solutions whose strength is such that a number of grammes equal to the formula weight is dissolved in one litre of water. If ra. so that If of the solvent we suppose that the we have salt does not alter the properties Let us first suppose that the solvent is water . strength of many substances. substituting these values we get W Raoult. and X = 80 x 4 2 x io . 324. 1886. unity .be the pressure due to the molecules salt in the solution.
tion of the properties of the solvent by the addition of the It would also take place if there were any chemical salt. on the more . action between the salt and solvent of such a nature that is heat is evolved when the solution the solvent is diluted.54 Raoult found in this case that 80 C. In this case Raoult found W  39. Raoult found that the effect of dissolved salts freezing points of acetic acid and benzine was much regular than their effect on the free/ing point of water. was 4'9C. and A= 29 x 4/2 x io p = 9 lowering of the freezing point of a solution of the same strength as before is When = the solvent is benzine. X = 44'34 x 42 x io 7 = io$ and #=290. (Landholt and Bornstein Tabellen) p substituting these values we get for the lowering of the freezing point of any solution of the same strength as before When acetic acid. 7 . 275. so tnat ^e 80=.
while the water of the current. the lower half again dipping into acidu lated water. In this battery the two electrodes are covered with finely divided platinum. as where the chemical changes seem on the whole to be the least complex. THE CONNEXION BETWEEN ELECTROMOTIVE FORCE AND CHEMICAL CHANGE. will increase will gradually during the passage . say hydrogen. say oxygen. If the electrodes are connected a current will flow through the battery and the hydrogen and oxygen above the electrodes disappear. THE principle that when a system is in equilibrium the Hamiltonian function is stationary can be applied to determine the connexion between the electromotive force of a battery and the nature of the chemical combination which takes place when an electric current flows through it. the upper half of the other electrode is surrounded by some other are well gas. the upper half of one is surrounded by some gas. while the lower half dips into acidulated water .CHAPTER XVII. We shall begin this is the case by considering Grove's gas battery. 132. The two electrodes coated with hydrogen and oxygen respectively.
disappear and an electrochemical equivalent of water The systems whose mean Lagrangian functions (i) the (3) change during this process are hydrogen above one electrode. condenser. these plates being made of the same material. will will appear. other. is %L H The mean Lagrangian where function for the oxygen is rjL . Let . electricity flows 1 Then if unit quantity of positive from the plate of the condenser which connected with the hydrogen electrode through the cell to the other plate.suppose that the electrodes are connected with the plates of a condenser Avhose capacity is C. be the quantity of positive electricity on the plate of the condenser connected with the oxygen electrode. by Faraday's Law an electrochemical equivais hydrogen will appear at the electrode covered with oxygen and one of oxygen at the electrode covered with hydrogen the hydrogen and the oxygen will combine and the result of the passage of the unit of electricity will be that an electrochemical equivalent of hydrogen and one of oxygen lent of . The mean Lagrangian function for the condenser is ^& C' 2 The mean Lagrangian where using the same function for the hydrogen notation as hitherto. and be the masses of the hydrogen and oxygen above let t]. (2) the the oxygen above the and <2 (4) the water. the electrodes and of the acidulated water respectively.
(240).1 eqiuvcucm ui is carried to and combines with the hydrogen at the other electrode. and ea are the electrochemical equivalents of hydrogen and oxygen. function is Hence by the principle stationary when there is ~ that the Hamiltonian equilibrium we must have ~ < # ^LH) is 6 ^ ^Z ) + ^ + ^ ^Z') " e s) C > the potential of the plate connected to the oxygen electrode exceeds that of the one connected to the hydrogen electrode.IL CIL oxygen unu cic^uuuc. we have by 83  Zw where T is the mass of the aqueous vapour. hence P=If e. be the mean Lagrangian function of unit mass of aqueous vapour above the acidulated water and in equilibrium with it. wmic LUC ejLecu. and T? diminished by e and 2 respectively. which but <2/C" the amount by which we shall call /.uunemica.). ^ (&)  e 2 ^r (i)L ) + (e. + ej .  ^(Z. while has increased < I by (e 1 + e a ). in other words it is the electromotive force of the battery. Thus if e. the net result of the process is that Q has increased by unity. and p Substituting these values in (240) we get .
case of the Gas Battery.But and by (83) is e. if and (242) are not confined to the p is can prove in a similar way that the electromotive force of any battery where the We solutions used are dilute. Equations (241) 133. ' B Thus if we know q.o/.(e. determine so that force of a cell way in which/ depends upon 6 we can by measurements of the electromotive and the variations of this force with the temthe perature we can calculate the mechanical equivalent of the heat developed in the combination which takes place in the cell. of the form Lastly is A'B + SO log 0. we making these substitutions we see where hence we have A = A' + e R l l log p . + es) w/ the loss of potential energy which occurs when an electrochemical equivalent of hydrogen combines with one of oxygen and may be measured by the quantity of heat developed by the combination of an electrochemical equivalent of shall hydrogen denote it by at the zero of absolute t q. + e2 w 2 . } temperature. then .
..c. cra . hence by (243) we have Now ew and eg are the mechanical equivalents of the heat developed by the same combination when it takes place at the temperatures 6 and absolute zero respectively.^.ui mubc buusuuices winca uisappear as me cnemicai action which produces the current goes on.. or in other words QdpfdO is the mechanical equivalent of the heat which is reversibly generated when unit of electricity passes through the cell. nq is the mechanical equivalent of the heat which would be evolved at the absolute zero of temperature by the chemical action which takes place when through the cell. a. while oj.. are the masses in unit volume of those which appear.. Helmholtz's principle (48) OdpfdQ is the heat which must be supplied to the cell in order to keep the temperature constant when the unit of electricity passes through the cell..d. Now^ the work done in driving this quantity of electricity through the cell plus QdfldQ the heat reversibly generated must be equal to ew the heat equivalent of the chemical action which takes place in the cell... unit of electricity passes From this equation we get as before By v. and the difference between these quantities must be the differ . divided by the molecular weight of the substance. are the ratios of the electrochemical equivalents of the substances to that of hydrogen.
attended by the production of an amount of heat comparable with that which occurs when is If the combination hydrogen and oxygen combine. e their electrochemical equivalents. of a large quantity of heat when the combination is attended by the evolution we may at ordinary temperature . hence since the temperature and then and spend (e/3 + e/ ) balance of work in our favour tq 4 must be the same both cases. gramme is compared with which of substance. 1} at zero and raise them to 9 degrees and then and with . if we start ea e 4 3. ) so that the net result in our favour will be ew If (e. then ff^d^jdO which is comparable with the heat required to raise the temperature of the substances degrees and is therefore at the most a few . to we should gain in units of work. 2 hundred so that calories per q.^ + e/a B units of work and gain ew by their combination. will be small measured by thousands of calories. we shall in raising the temperature spend (e. we have and therefore by (245) d e* *4~( But by (241) SO that B = e/ 3 + / ~ 4 e/!  e/2 (246). we let them combine at zero raised them. A B let them combine.of the specific heats at constant volume of these gases.Cj + /2 ) 0.
which is often employed. combining this with (245) we get .e. then since any small change cannot alter the value of the mean Lagrangian function of the gases or dilute solutions when in equilibrium we get if we suppose the change is that . ca .. We see by this equation that when electromotive force increases as the temperature increases the electromotive force is greater. If k be the coefficient of the chemical combination cell. while when the be rigorously electromotive force diminishes as the temperature increases it is less than that calculated from the formula p = eg. which would take place through the solutions if unit of electricity were to pass Q^^RJlozk + Ae + JBGlogB + eq . (247). we see that whenever the combination leaves the number of molecules unaltered B will vanish and the equation will the true... J3. D.Since by Dulong's and Petit's law clt c2 .. C.. c4 are in versely proportional to the combining weights of the gases A. i. (115) which goes on in the the value of when the densities of the gases or solutions have the values they possess when in chemical equilibrium with each other.
Here if p and cr CuS0 4 and ZnSO 4 equilibrium volume of the is when there chemical log/e = log^r. equation (247) will at once give k. 3 cr p and ZnS0 4 when the so that if <r' are the densities of the CuSO 4 and the electromotive force is/ we have Now at oC. we should be able by equation ./?!# is nearly io 6 and/ is about io 8 so that 100. og72 cr or approximately since for ordinary strengths of solution "' log/)'/ is small compared with 100 = cr 200. for then if we measure the electromotive force and the densities of the Thus the solutions. Daniell's cell enables us to calculate the coefficient of the combination Zn + H 2 SO 4 + CuS0 4 = ZnS0 4 + H. hence we see that in this case when there is equilibrium practically all the sulphuric acid goes to the zinc.cell in which this combination takes place.SO 4 + are the masses per unit respectively Cu. If we determined the electromotive force of a battery when lead wire dipped respectively into acid solutions of lead nitrate and lead chloride. ).
.ri = = i x lo lo & I0 ^ i'i x 45 x 2'3 x 10" 7 '14 x io approximately....... so that the electromotive force is than the ninth of a gases volt. pz the electromotive force when the densities electrodes..... since e. = io~ 4 Rfl . AA=. By making diminished by rather less the densities of the small above the electrodes sufficiently we could reverse the electromotive force... when o are and or'. then we have by (249) A A = v*i If the densities of the oxygen and hydrogen were diminished one thousand times then at the temperature o C..u we return now to is tne nyarogen ana oxygen gas battery. We can easily deduce from this equation the way in which the electromotive force of a gas battery depends upon the pressure of the gases in the vessels above the If p l is the electromotive force of the battery the densities of the hydrogen and oxygen are p. p' respectively... The diminution rarefaction does not in the electromotive force caused by however deuend unon the magnitude . equation (247) for this case .. (249).i 'i x jo 10 .. though in the case when the gases are oxygen and hydrogen the rarefaction required would be more than could practically be obtained.
of be seen from table that the effect an batteries increase in temperature on the electromotive force of gas is very variable. 98). of oxygen and hydrogen diminishes the effect of rarefaction if the combination were to take place without condensation. The following table taken from his paper gives the electromotive force of a large number of batteries It will at 15 C. p. and of a few at 75 this 80" C. action of which would these values the electromotive force of the battery is zero. Experiments on the electromotive force of gas batteries charged with various gases have been made by Pierce (Wiedemanris Annalen. We see too from equation (249) that the electromotive force in all cases tends to produce a current the chemical make the densities. and the electromotive force is in one direction or the opposite according as there is more or less of some substance present than there would be if the mixture of gases or dilute solutions were in chemical equilibrium.might be practicable. vm. of the gases or dilute solutions approach the values they have when in When they have chemical equilibrium with each other. for of the five batteries whose at different temperathe electromotive forces of three were less and of two electromotive forces were determined tures. the diminution in the electromotive force caused by diminishing the density one thousand times would be about oneseventh of a volt. The condensation which accompanies the combination . . greater at the high temperature than the low.
this change favours the production ozone instead of oxygen when the current passes and so ncreases the chance of complete combination.ELECTROMOTIVE FORCE AT 75C8oC. for we see from the table that the substitution )f acidulated water for water between the terminals increases he electromotive >f force.0 2 water water 780 "954 875 where electromotive force of the hydrogen and oxygen gas = 34 x 42 x io 7 is less than that given by <=y he formula (246) even when the variation of the electroThis notive force with temperature is taken into account. dO dNO dCO The )attery water water water 828 '945 H and N O H and H. 1 8 2 . ieems most probably to arise from the arrangements being uch that the complete combination of the hydrogen and >xygen contemplated in the preceding theory would not ake place.
at o C. We can sometimes transform equation (244) by . The electromotive force in this easily seen to be in the where p and cr are the densities of the hydrogen two vessels.solution of hydrochloric acid between the electrodes. there will be an direction electromotive force tending to produce a current in this and equal to the increase in the mean Lagrangian function produced by the passage of unit of electricity. this equals io logp/o.approximately. 6 (or oxygen) the density in one vessel is e times that in the other the electromotive force will be onehundredth of a so that if volt. will terminals. 134. In fact when we have any arrangement in which the passage of an electric current in a certain direction increases the Lagrangian function of the system. THe gas battery will work even if we have the same it is at gas (say hydrogen) above the electrodes provided In this case on closing the circuit there different pressures. q in will be the heat in mechanical units given formula (244) out in the combination of one gramme of hydrogen with chlorine plus the heat given out when 365 grammes of hydrochloric acid are dissolved in a large quantity of water. but be no change in the volume of the liquid between the when the unit of electricity passes through the battery an electrochemical equivalent of hydrogen will transferred from the vessel where the pressure is high be to the one where case is it is low.
coiisuiuiing me uaicery would ue in equilibrium in the proportion in which they exist in the battery at the temperature 6. cr .. Then by (243) and by (246) . p. Gibbs 6 is the highest temperature at which the radicles can combine with evolution of heat. 388). and as it is not always possible .According to Prof.. 1886. then at ordinary temperatures the place when term on the righthand side of this equation will be small compared with the first and we may write equation (250) in the form An equation identical in form with this is given by Professor Willard Gibbs in a letter to the Electrolysis Committee of the British Association (British Association Report. while according to our view it is the temperature at would be which the chemical system forming the battery in equilibrium. o2 Subtracting these equations we get If a considerable quantity of heat is given out by the combination which takes last unit of electricity passes through the cell. .
are the electrochemical equivalents volume of the substances (A). (D} when o = 6. then by equation Now if MM I} s. there is equilibrium we have by equation (246) . (D).~ approximately. ^% r' *a 4 + A6 + B6 log & + tq. dp d9 We shall now investigate under at what conditions the it is possible to find a temperature shall be in equilibrium. (JD) respectively. (B}> (C).^0 log e s.v = . cra are the densities of (A). (B). if <? e# <? c1} ca ca c the specific heats at constant . (B). If p 15 pa oj. which the system would case of We consider the equilibrium of four substances (A). Now and . MV MI are the molecular weights of the substances . (246) so that ( C}. (C).
tion in When a + l<: + d. when there is no change volume on combination. positive. .> for any arbitrarily chosen set of values of P2 ! V V 3rd case.e. In this case as B increases from } zero to infinity p ap a 6/<r c<r a<e ranges from zero to C. \! is the heat given out when the e<7 quantity of (A} decomposed by one unit of electricity combines with the equivalent Let us first suppose that this quantity is quantity of B. so that again as p^pa/f^f^ never exceeds a certain maximum it is not always possible to find a temperature which should be one of equilibrium P. When a+ b<c+d. nf hpnf i> is in crpnprnl onlv possible to find a tem . a b c l } there is a diminu volume In this case as 6 increases from zero to infinity. when after combination.e. 2nd case. i.e. i.a A ((t+6~cff) P " C ge f^=C6 "l *i C ****.<rf also increases from zero to so that in this case it is always possible to find a temperature which should be one of equilibrium for any arbitrarily We see chosen set of values of p lt p 3 o^. and consider the following cases. i. and therefore since it never exceeds C it is not always possible to find l arbitrarily a temperature which should be one of equilibrium for any chosen set of values of p l} p s) cr l} <ra . infinity p p 2 /o. when In there is an in crease in volume after combination. When a + b = c + d. this case as in reaches a creases from zero to infinity p 1 V// tr i Ccr/ starts from zero then maximum and decreases again to zero. o2 too that when the combination is attended with an . in ist case.
. increase the temperature will temperature still further. In these cases where pfpf/ofa^ has a this maximum value at a finite temperature the mixture of gases after passing for any promote combination and produce an evolution of heat which will increase the temperature in will be in an unstable state.Summing up the results of this investigation we see that equation (250) can only in general be applied to cases where the reaction producing heat is accompanied by a diminution in volume.
The reason we can not reverse every process is because we .CHAPTER XVIII. then irreversible processes must be capable of being explained as the effect of changes all of which are reversible. effect of WE have hitherto left out of consideration the such things as frictional and electrical resistances which destroy the reversibility of any process in which they play a part. If however we take the view that the properties of matter in motion. IRREVERSIBLE EFFECTS. But if every physical phenomenon can be explained by means of frictionless dynamical systems each of which is reversible. by means of ordinary dynamical systems involving on this view. 135. It would not be sufficient to explain these irreversible effects friction. then it follows that if we could only control the phenomenon in all its details. the irreversibility of any system is due to the limitation of our powers of manipulation. as friction itself ought. are sufficient to account for any physical phenomenon. as considered in abstract dynamics. so that as was pointed out by Maxwell. it would be reversible. to be explained by means of the action of frictionless systems.
and whose mean is what we actually are therefore at liberty. which may be quite unlike the In consequence of actual effect at any particular instant.We are not only unable to manipulate very minute portions of matter. The finite time our sensations last causes any phenomenon which consists of events following each other in rapid succession to present a blurred appearance. so that what we perceive at any moment is not what effect but merely an average is happening at that moment. if it is more convenient observe. but we are also unable to separate events which follow one another with great rapidity. and let us assume at first that the motion is represented at each in. just as the finiteness of the wave length of light prevents us from seeing any separation we it Thus if between two points which are very close together. to look upon any effect as the average of a series of rapidly changing effects of a different kind. We for the purposes of explanation. It might appear at first sight as if we could explain the . the fmiteness of the time taken by our senses to act. instant by the equations with these terms so that the dynamical equations are not equations which are merely true on the average. we are incapable of separating two events which happen within a very short interval of each other. observe any effect we cannot tell by our senses whether represents a steady state of things or a state which is rapidly changing. Let us is now such that in consider the case of a system whose motion order to represent it factional terms proportional to the velocity have to be introduced.
however. the same as ' that given dT\dx. this. For this to be the case.~ "dt ~dlc LtfV CdtAf ~ d Ct'Jv ~ It iifv + ~dx CvtAf = fa UtAf external force of ~dic CCtAf thus the term _ dt dx dx must be equal to the "frictional term" which is proportional to x. If these two expressions are identical. If we investigate the case of a vibrating piston in confrictional nexion with an unlimited volume of air. dT' jdx for all values of x. which inconsistent Avith the condition necessary in order that the motion of the subsidiary system should give rise to the "frictional" terms. must vanish is by the ordinary expression in Rigid Dynamics. however. that is. it is evident that T' must involve x. T' cannot involve x. when it is bounded by fixed obstacles the waves originated by the piston get . The momentum of the system and this momentum must be is. T'}\dx. d(T+ viz. Hence we conclude that the terms cannot be explained by supposing that any subsidiary system with a finite number of degrees of freedom is in connexion with the original system. we shall find that the waves starting from the piston dissipate its energy just as if it were resisted by a frictional force proportional to its velocity . is only the case when the medium surrounding the piston is unlimited.
but not the motion at any particular instant. with a term included expressing a resistance proportional to the velocity. Again. and this might on the average be repre. loses sented by the introduction of a term expressing a resistance varying as some power of the velocity . but only when the average is taken over a time . nor when it was moving freely and not in collision with any of the molecules. the connexion must be such that energy can flow from the original into if the subsidiary system. the kinetic theory of gases shows that the equations of motion of the gas. neither when the body was striking against a molecule of the gas. the frictional terms are to be explained by a subsidiary system in connexion with the original one. Hence w. to take an example. it will be constantly losing momentum. Thus. when they contain frictional terms.air to the piston. if we take the resistance to motion in a gas which arises from its own viscosity. with this term in.e conclude that the equations of motion. but not from the subsidiary into the original system. while. would not be true at any instant. are not true at any particular instant. represent the average motion of the system. Inus the motional terms cannot be explained by the dissipation of the energy by waves starting from the system and propagated through a medium sur rounding it. since the body by its impacts with the molecules of a gas more momentum than it gains from them. but the equations of motion. for in this case it would be possible for energy to flow from the subsidiary into the original system. let us suppose that we have a body moving rapidly through a gas then.
repeating its value n times shall for brevity speak of each of the in a second. value. then vanishes.or a last system which is subject to the action 01 torces wnicn only for a short time but which recur very frequently. in the case of a when value. and shall call second. then vanishes. the body it when however small that error. and so on. Let us suppose that in the expression for the Lagrangian function of the system we are considering there is a term It has for some small time a L! which is intermittent. For example. has a finite body is free from collision L' is so may be assumed to be zero without appreciable is in collision with a molecule L' the is. molecule represents the action of a collision. oc dt ~dx dx dt dx dx Integrating this equation over a time r T we get o dt '~\T o dx dx _dx dx is steadily changing \dL'ldx\a will either vanish or be exceedingly small. so that in general Now unless the structure of the system we may neglect it and write . if Lagrange's equation corresponding to the coordinate L is the steady part of the Lagrangian function. epochs during which the function L' has a finite value as finite We n the number of collisions per body moving through a gas L' may be the part of the Lagrangian function which a of the gas on the body. then springs into existence again.
changed
in
if
it
by a
finite
amount.
Now
T be the time a collision lasts
and
if
there are n
of them per second
'
iL'
,
rdt
(252);
if as in
a
numerous
class of cases
collision,
remain constant during the
~
x may be supposed we may write (252)
j
to
as
*

fl>
JL
,
dx
where
Since
dx
X=
T
[ Jo
fd_
dJL
_ dL\
doc)
\dtdx
\dt dx
/^ dL _ dL\ dx)
'
equation (251) becomes
d dL
dtdx
dL _
dx
dx'
these intermittent forces
Thus the same
force
X
is by would be produced by a steady of type x and given by the equation
the effect produced
as that which
X=n&. ax
Y
Similarly they would produce the same of type y where
effect as a force
Y=n%. dy
If n does not involve the coordinates x,
re
y
explicitly
then
have
dY_dX ~
dx
le
.....................
dy
(253 ''
consequences of this equation will be similar to those
44.
for example suppose we were to decrement of the torsional vibraions of a wire depended on the extension of the wire, then would follow from (252) that when the wire was vibrating ;iere would be a force tending to alter its If the length.
eveloped in
Thus
nd
that the logarithmic
:
ictional resistance
to
the
torsional
vibrations
were
p.0,
'here 6
ire,
the angular velocity of a pointer attached to the then if the above equation is true, there would 'be a
is
jrce
X
tending to lengthen the wire and given by the
quation
dX = ~ zdu,. w " ere x
'
1S
"ie
,
rfft
ff
Thus
if/ is constant,
ax
we have
Whence
adinal
it
follows that if the torsional vibrations were
eriodic there
would be a force tending
;
to
produce longi
or again, if the of half their period iscosity of an iron wire were altered by magnetization lere would be a periodic magnetizing force acting on a
vibrations
ibrating wire
whose period would be half that of the
(253)
is
)rsional vibrations.
The
relation
only
satisfied
when n
is
in
288
DYNAMICS.
dY dX _
dx
instead,
y.
d\og n _
dy
dlog n
dy
dx
z,
and
if
we
consider forces of a third type
the
two additional relations
dX _ dZ _
dz

dx

7 d\Qg n dx
d log n
dz
dZ   dY _ Y d\Qgn
1
_ dlvgn /,
dy

dy
so that
dz
dz
dY , r (dX dX\ + Y v (dZ dY\  dZ\}+X(: rJ^ =0...(254). dz dx
,

dx
)
(
dy J
\dz
J
\dy
J
v
;
In these relations X,
Y,
Z
are only those parts of the
forces of types x, y, z which are intermittent in their action. If
number of collisions
x,
from the nature of the case we can see that the is independent of some one coordinate
it
then
follows from the above equations that
/dY
dX,
i/rfZ
dX
If the viscous forces arise from collisions with several
distinct systems, instead of with
one as we have hitherto
assumed,
we
shall
have
_
dy
but
if
7<!
dx
'
,,
2
involve the coordinates x, y, then the relation
(253) must be replaced by one involving higher differential
coefficients.
The preceding
considerations
show
to
that in those cases
where the viscous forces are due
"collisions"
we have
several criteria the fulfilment or nonfulfilment' of which will
afford us information about the constitution of the system.
Thus
if (252) is not fulfilled we conclude that the number of collisions depends upon the value of the coordinates, if
(253)
is
not
fulfilled
due
to collisions with
There
of various
is
a great
we conclude that the viscous forces are more systems than one and so on. dearth of experiments on the influence
conditions on viscous forces except these forces are those which resist the passage of It does not seem probable electricity through conductors.
physical
when
however that
in this case the resistance
can be due to a suc
cession of impulses whose number is proportional to the strength of the current; for the case is not analogous to
that of a viscous force depending
on the change of shape
or configuration of a system, where we might reasonably expect the number of effective collisions to be proportional to the velocity of the change.
In order to get some idea as to how discontinuous forces can produce the effect of electric resistance, let us
consider
are
some
cases in which effects analogous to resistance
produced by a succession of changes following one another in quick succession. A very good example of a
which by means
of a tuning lork interrupter
me
plates 01 a
condenser are alternately connected with the poles of a If the rate of discharge is battery and with each other. this arrangement of condenser and tuning fork
very rapid,
produces the same
effect as
a resistance
i/uC where
C
is
the capacity of the condenser and ?i the number of times it Thus in this case a combination is discharged per second.
of induction and discharge produces the same effect as a resistance. Another case in which the conditions are plainly discontinuous but which produces the same effect as. a
continuous current,
rapid,
filled
is
if
the rate of alternation
is
sufficiently
when
air.
electricity passes
with
through a closed glass tube If electrodes are fused into the tube and
electrical
connected to an
machine
in
action there will
be
no discharge
of electricity across the
tube until the electro
motive force gets large enough to break
strength of the
down the
electric
air, when a spark will pass, an interval will elapse before the second spark passes, during which the electromotive force inside the tube will be increasing to the
value necessary to overcome the electric strength of the air. If this interval is very short then the successive discharges
will
produce the same
effect as a
continuous current through
the tube.
The
consideration of this case
may
also
throw
some
light
effected,
on the mechanism by which the discharge is for there are .many reasons for believing that in
is
this case the discharge
accomplished by the decomposi
tion of the molecules of the gas, the energy required for this decomposition coming from the electric field, and the
consequent exhaustion of the electric energy producing the
between their chemical properties than their physical ones, .and the difference between a chemical and a physical process seems to be that in the chemical process the molecules are split up while in the physical one they are not. In many cases there is direct evidence from both (2)
spectroscopic and chemical analysis that this decomposition takes place, and again gases of complex composition whose molecules are easily split up are also electrically very
weak.
(3)
We
can explain by
Soc. v.
this
(Proc.
Camb. Phil.
400)
hypothesis in a general way why the electric strength
.should gradually diminish as the gas gets rarer and rarer, until when the pressure is about that due to a millimetre
pressure
of mercury the electric strength is a minimum, when the falls below this value the electric strength increases
again until at the highest exhaustion which can be got by the best modern air pumps the strength is so great that it
is
almost impossible to get a spark through the gas. Dr Schuster has shown (Proc. Royal Society, xxxvu. (4)
318) that the electrical discharge through mercury vapour
p.
is supposed to be a monatomic gas presents a peculiar appearance and passes with great difficulty, and
which
quite recently Hertz (Wied. Ann. xxxi. p. 983, 1887) has shown that the electric discharge passes more easily through
light
a gas when it is exposed to the action of violet or ultraviolet than when it is in the dark ; since ultraviolet light has
a strong tendency to decompose, the molecules of a gas through which it is passing, this is very strong evidence in
favour of the view that the discharge
is
caused bv the
in other words the quantity of electricity E which flowed through the tube was proportional to the excess of the electromotive force above that which broke the dielectric down. Soc. p. Soc. Some experiments . is discharges in the horizontal direction by passing a vertical discharge through it. this seems to indicate that the electromotive force JE produces a supply of atoms in the nascent condition and that the rearrangement of these atoms discharges the field. a very small electromotive force sufficient to produce a current in a region of the gas screened off from the electrical influence of the primary disAgain Hittorf found that a gas was weakened for charge. XLII. Again in Mr Varley's experiments on the through gases (Proc. The diminution in the electric strength of a gas after the passage of a spark can be accounted for in the same way. xix. insulators the insulation for low electromotive forces is not as in the case of gases perfect. A dielectric always leaks condenser the plates of which are separated by a liquid however small the difference between the potentials of the plates may be. that (Proc.without further decomposition. In the case of fluid. Roy. 371) Thus Dr Schuster has shown when a strong electric dis charge passes through a gas. 236) the quantity of electricity which passed through a tube filled where is the difference with gas was proportional electric discharge to E a constant between the potentials of the electrodes and electromotive force. Roy.
This indicates that the leakage is produced by the rearrangement under the electromotive force of that this condition if it first some molecular condition. though they only conduct pure. of the molecules of the salt by the electric field. yet when salts or other substances (which may themselves be nonconductors) This kind of conare dissolved in them. which is just what we should have exif the electric field split up the molecules of the fluid. or else by the rearrangement when in a nascent condition of the atoms of a molecule of the salt or the constituents of a more complex . There are many liquids which. the discharge of the electric field which constitutes conduction must in some way in it. for were the leakage would vary as a higher power than the of the electromotive force. Quincke. using however electromotive forces comparable with those which would produce sparks through the dielectric. found that under these circumstances the quantity of electricity passing through the dielectric varied as a higher power than the first of the pected electromotive forces. electricity with great difficulty when duction is which are not observed called electrolytic and is accompanied by eifects in other cases. conduct readily. who investigated the passage of electricity through the same liquids.difference of potential between the plates. or other be due to the action of the substance dissolved The consideration of the discharge through gases as well as the chemical decomposition which always accompanies this kind of conduction suggests that in this case the discharge is caused either by the splitting up. and is not produced by the electric field. Since the solvent is not a conductor.
312) have great. The forces between the atoms in a molecule are usually .. I have lately made some experiments on both these effects to detect that the slightest change and have not been able was made by the current. whilst from the evidenceof many experiments it seems clear that the smallest electro motive force electrolyte. Fitzgerald and is Mr Trouton obeyed with (Refort of the British Association Committee on Electrolysis. electromotive force had to break up the molecules the current would be proportional to a higher power than the first of the electromotive force. so that if number of separate systems is increased by the passage of the current these effects ought to be increased by the passage of a current through the solution. just as to send a spark through a gas. Now the of the solution in an osmometer and the lowering of its vapour pressure depend upon the number of molecules in unit the volume of the liquid and not upon their kind. exactness shown that Ohm's Law by a whereas if the current flowing through an electrolyte. (2) is sufficient to start a current through an The experiments of Prof. that the splitting For these reasons we conclude up of the molecules which allows the current to pass is not caused by the electromotive force but takes place quite indepen dently of the electric field. p.(1) If it were true it motive force to start a current would require a finite electrothrough an electrolyte. 1886. (3) If the molecules were split up by the current then of individual systemsit the salt will form a greater number when rise the current is flowing than when is not.
and there is it nothing to prevent our supposing.In order to form a definite strength of the electric field. for all that is necessary on this view for the passage of a current is that the molecules of the electrolyte should split up. the electric force due to which neutralizes in the region between the layers the external electric force.n<.<=> rrnrl vpf hnvp rnnh'rmnl . The positively charged molecules soon come into the neighbourhood of some negatively charged ones travelling in the opposite direction and they recombine. in way we get two layers of positive and negative electricity formed. thus the due to the layers vanishes and the external electric field is reestablished to be soon demolished again by the decomposition and rearrangement of other molecules.R small tic WP time the atoms remain which they are combined. idea of the way in which the field gets discharged we may take the usual view that the constituents into which are the molecule splits up of electricity. if other reasons render probable. the this negatively charged one in the other . And since the state of dissociation depends upon the ratio of the dissociated to the time during mav mnlfp this n. and that when charged with opposite kinds the molecule splits up the positively charged constituent travels in one direction. we nlp>. this does not necessarily imply that the electrolyte should when free from electromotive force be largely dissociated. Although we suppose that the current is transmitted by the molecules of the electrolyte breaking up. that they would instantly reunite if no electromotive force acted upon them. while the negatively charged ones do the force same with some positive molecules.
accomplished in a fundamentally different way from that For the chief differences through gases and electrolytes.
between conduction through metals and through
electrolytes
are (i) that in electrolytic conduction the components of the electrolyte appear at the electrodes, and we have polarization,
and
(2) that the conductivities
of electrolytes in
crease while those of metals diminish as the temperature
increases.
Let us begin by considering the
that of polarization.
first
of these differences,
A little
consideration will show that
we
could hardly expect to detect it in the case of metals or alloys, for here instead of, as in electrolytes, the property of splitting up being confined to a few molecules sparsely scattered through a nonconducting solvent, the whole of the molecules can split up, thus the rate of disappearance of
any abnormal condition would be almost
than in the case of electrolytes, so that
if
infinitely greater
any polarization were produced it would probably die away before it could Let us next consider the appearance of the be detected.
constituents of the conductor at the electrodes.
The
only
case in which
alloys,
we could expect
in
this
to detect this
is
that of the
but
even
case
Prof.
RobertsAusten was
unable to detect any change of composition in the alloy round the electrodes; we must remember however that an alloy differs very materially from an electrolyte because
while
in
the
latter
we have
a
few ''active" molecules
it is
embedded
in a nonconductor, in the former
as if the
solvent as well as the salt conducted, so that the discharge is not concentrated on a few molecules of definite com
general are subject to exceptions, thus the conductivities of selenium, phosphorus and carbon increase as the temperature increases
;
that of bismuth
is
said to increase at certain
temperatures, and I have lately found that the conductivity of an amalgam containing about 30 per cent, of zinc and
remember too
increases.
is must greater at 80 C. than at 15 C. that the rate of increase of conductivity with temperature for 'electrolytes diminishes as the concentration
70 of mercury
We
No
drawn
between
sharp line of demarcation can therefore be the two classes of conductors on this
account.
and
There does not seem any difference between metallic electrolytic conduction which could not be attributed
number of molecules taking part in metallic conduction, whilst assuming that in all cases the current consists of a series of intermittent discharges caused
to the vastly greater
by the rearrangement of the constituents of molecular
systems.
We
leads.
shall therefore
results to
proceed to examine the dynamical which such a conception of the electric current
Let us consider the case of an electric
electromotive force
is
field
where the
Let
the electric
everywhere parallel to the axis of x. displacement in this direction be f, then in
is
the Lagrangian function of unit volume of the the term
medium
there
K
_
parallel to the axis of
x.
K
In consequence of the continual rearrangement of the molecular systems f/J^ is not uniform but keeps alternately vanishing and rising to a maximum
value.
If these alterations are sufficiently rapid the effect
this
represented by
force equal to
term will be the same as that of a steady
value, that
is
its
mean
to
Let us suppose
that T
is
that in consequence of the rearrange
ment of molecular systems/vanishes n
times a second, and
the period which elapses between the end of one period of extinction and the end of the next, then
A
where
i is
the
maximum
value of f, and
ft
a quantity which
is
depends upon the
ratio of the
time the field
destroyed to
that during which it exists. When the molecular systems rearrange themselves so as to discharge the electric field molecules charged with f
units of electricity pass through unit area in one direction, while f units of negative electricity are carried by molecules
moving in the opposite direction. Thus 2f is the sum of the positive electricity moving in one direction and of the negative in the opposite passing
through unit area in unit time,
it
is
therefore equal to
u
is
where u
the intensity of the current, and since equal to unity, the force we are considering equals
is
m
Ihus the greater the number of times resistance ZTrp/nli. per second the displacement breaks down &c., the better
the conductivity.
Now the breaking down of the displacement is caused by the rearrangement of the molecules, and the rearrangement of the molecules in a solid will produce much the
gas,
same effects as the collisions between the molecules of a and will tend to equalize the condition of the solid,
thus
we might expect
to increase with the
number
the rate of equalization of temperature of molecular rearrangements.
electrical conductivity would also increase in the same way, so that this view fits in with the correspondence which exists between the orders of the metals when arranged ac
The
cording to thermal and to electrical conductivities.
The preceding investigation of the resistance of such a medium is only valid when the electromotive force is approximately constant over a time which includes a great many discharges. If the displacement were to be reversed
during the interval between two successive rearrangements of the molecules the substance would behave like an insulator
and not
like a conductor.
If
a is
the specific resistance
of the substance then
27T/3_ =
^
"'
nS
where
all
27T/3
^f'
we know about
than unity.
To
be greater ft is that it cannot find a superior limit to n let us assume
According to the electromagnetic theory of light the electric displacements which constitute light are reversed
number
times per second; comparing this with the nearly io of times the field is discharged in an electrolyte, we
16
see that the displacement would be reversed many times a second before it was discharged and hence that such
substances would behave like insulators to these rapidly alternating displacements, and so according to the electromagnetic theory of light should be transparent, which as a
matter of fact most of them
overestimated
jB
are.
Again,
we have
that the
certainly
and probably underestimated K;
if
this into consideration
we may conclude
discharged
is
we take number
of times the field
is
probably even in the
greater than that calculated on the assumption that their'conductivity is the same as that for steady currents.
The number
will
of times the field
is
discharged at any point
depend upon the number of molecules which split up in unit time and the distance which these travel before If m is the number of times the molecules combining. in unit volume split up in unit time and if it requires q
molecules per unit area to be split up in order to discharge the field, then if the molecules after being split up travel a distance x under the influence of the electromotive force
before again entering into combination,
we
shall
have
n=
since any g molecules
m
x,
?
on
n
either side will
which break up within a distance x\z discharge the field. Since both x and q
to
if
it,
will
be
directly proportional
will
be independent of
is
the electromotive force, the splitting up of the
molecules
Since
accomplished by other means.
u

zni =
2
ff
xf,
and
since, if the substance is
f
an electrolyte,
=6,
where
e is
the charge on either of the ions into which the
splits up,
molecule
we have
u=
2inxe.
salt in
So that
unit
if
^be
the
number of molecules of the
volume
merely to use this conception of a of The view is of a substance according to specific resistance 27T/3 our nK' and if this varies when the circumstances are /?. or by the number of times a second the molecules up. altered specific inductive capacity being strain altering the split by strain. But u\zNi is. which current to deduce reciprocal relations from the effects various physical agencies on resistance. the quantity called by Kohlrausch the sum of the velocities of the ions. given by view of the would lead. To take an example the resistance of a metal wire seems to be this may arise either from the slightly affected by strain. Report on Electrolysis.to the same expression in unit for the absolute distance travelled by each ion time as that given by Kohlrausch. see 35. A full discussion of this would however lead us too far is from our purpose. to a force eaual to . p. and if we assume current that the ratio of the velocities this is experiments on the migration of the ions. may be because either n. British Association Report. 1885. or finally by an alteration in the time the field remains discharged. The term 2 27T/ ~~K~ in the Lagrangian function corresponds.second. or K are changed it changed. see Lodge. 755.
the strain there would be no corresponding elastic force. If however it does arise from the alteration of with the K strain the mean value of the elastic force is d and Jo 2 /V/ = af = a^. Thus the mean value of the elastic force ftn de For good conductors this term of it will be exceedingly small see the table p. 300. x is a coordinate of any type this term indicates a force of type x equal to ft n dx or as it may be written 2m8 2 fix . will never get large enough produce an appreciable change the large forces required to in the extension. on account of the smallness and even for bad conductors to make it comparable with If cr/n. and which like /3 depends upon the time the field remains discharged. n2  ' where a is a number which cannot be greater than unity.
used in experiments on . hence we conclude that the reciprocal effects corresponding to the effects observed on the resistances are probably much too small to be capable of influence detection unless for very bad conductors under the of electromotive forces comparable with those static electricity.a 1 w _ d\0%K and so is exceedingly small .
effect of. article on electricity quoted. liquids. 173 Absorption of gases by liquids. 221 : effect of. 136 magnetism quoted. 181 on electromotive force required to decompose an on on on on on on electrolyte. 240 effect of temperature on. 186 Affinity. effect of chemical equilibrium. 162 solubility. density of salt solutions.INDEX. residual torsion. membranes for osmometers. effect of. 203 Baur. Battery. effect of Berthelot. electromotive force 265 Gas. 203 192 Chrystal. 200 Bosscha. 65. 101 Chemical equilibrium. 221. effect of on vapour pressure. 259 Bidwell. specific inductive capacity. absorption of gases by Capillarity. igi dissociation of gases. 14 Adie. determination of coefficient of. 234 237 effect of magnetization on. 271 Alloys. 95 Absorbed air. forms of clouds. 130 on dissociation. 275 temperature on magnetization. effect of. effect of. 105 Law of Maximum work. 54 Boltzmann. 161 Bevan. 87 effect of. 262 163 Cassie. Young's modulus for ice. electric resistance of. vapour pressure. Absolute temperature. Least. effect of. 220 Bertrand. 251 255 freezing point. 215 effect of pressure on. 61 . 179 Henry's Law of. Bnnsen. 234 237 temperature on. . 181 Action. by the observation of the electromotive force of a galvanic cell. 237 effect of surface tension on. effect of magnetization on the length of an iron bar. 296 of. vapour pressure.
293 Discharges. number of. effect of moving conductors on stiffness of.Constitution of bodies. io<5 effect of. 208 Boltzmann on. "9 "unconstrainable. 221 of electricity on. 210 of salts in solution. 293 32 pressure. 164 specific heat of. 19 " kinosthenic. 207 presence of neutral gas on. electric. effect on vapour pressure. 300 Dissociation. on vapour pressure. 41 mechanical force between. through liquids. 20 Critical value of "speed. 291 Electricity. effect of pressure on. on vapour 167 . Maxwell on. 94 134 Coordinates. 161 Dynamical interpretation of temperature. 56 of. induction effect of. 175 effect on freezing point. 43 Electric resistance. 262 Dupre. 43 electromotive force with temperature. variation of elasticity of wires. 182 Discharge. 99 Dielectric." 94 magnetic force. definition of. 40 on Czapski. 133 Controllable coordinate defined." 9 "positional. 212 Dissolved salt. inertia of. 62 38 Diffusion of salts. 207 204 effect of temperature on. Currents. 201 of a solid into two gases. 29 1 through liquids. 193 of nitrogen tetroxide. 200 effect effect of effect of surface tension on. 200 Willard Gibbs on. 200 of phosphorus pentachloride. 289 Electric discharge through gases. through gases. effect of current on. 90 Elasticity of a wire. in electric field. strain in due to electrification." 12 specification of.
275 Energy. 116 237 magnetization on. due to currents. chemical. 257 effect of torsion on. 168 effect of pressure on. 85. effect of strain on magnetization. magnetic field. 168 .pose. produced by inequalities 106 of batteries. 69 magnetic. 68 Free energy. 265 of gas batteries (table of). 87 Electrolytic conduction. effect of capil' larity on. on Hall's phenomenon. 87 required to decompose an electrolyte. force on soft iron in magnetic field. 262 Gas. 239 effect of pressure on. effect of pressure on. 260 effect of surface tension on. due to variation in magnetic field. 221. 55 magnetic force. 158 effect of strain on. 262 effect of dissolved salt on. 71 required to decompose an electrolyte. 47 Fitzgerald. "free. 215 effect of strain on. 95 259 Freezing point. 162 effect of electrification on. effect of pressure on. 157 Equilibrium. 47 a conductor carrying a current. 240 temperature on. 84. 234. 293 Electromotive force due to variation of the magnetic field. 22 1 effect produced by flow of heat in a Evaporation. Latrraneian function for a nerfect eas. 294 Force on a body in a magnetic field." 95 Entropy. 73 on Ohm's law in electrolytic conduction. critical value of 56 hysteresis. effect of effect of v. Ettinghausen and Nernst. 68 produced by twisting a magnetized wire. 164 Ewing. iu . 68 electromotive. 104 Faraday. 87 in temperature. 172 effect of surface tension on. 238 effect of surface tension on.
on Hall's phenomenon. 37 "freie energie. 23. van t'. residual Induction of electric currents. Larmor on varying action. 56 Kinosthenic coordinates defined. 175 osmotic pressure. expressions for." 95 variation of electromotive force with temperature. 269 strain produced by a magnetic field. 152 liquid or solid. 65 Irreversible effects. 2 objection to Weber's law offeree between two electrified spheres. 188 v. pressure in dilute solutions. i. 302 field. action of light on the electric discharge. conservation of energy. variation of electromotive force with temperature. 18 Law. on chemical equilibrium. I4 ? 1 mean value of stationary. 146. strain produced by a magnetic Kohlrausch. 52 Hertz. 29 145. 206 charge of a Leyden jar. 281 Jahn. chemical equilibrium. 14 Leyden jar. 32 magnetism. second. 41 Inertia of electricity. 9 Height to which a salt solution rises in an osmometer. 99 Least action. Helmholtz. 73 Groves gas batteries. elongation of a bar produced by magnetization. 104 effect of walls of vessel Hopkinson. of Thermodynamics. 225 Hall's phenomenon. 52. 155 .. 266 Guldberg and Waage. 59 effect of magnetization on the volume of a magnet. 136 expression of a gas. 136 Horstrnann. J. discharge of electricity through gases. 188 on chemical action inside. 99. electrolytic conduction. 54 Lagrangian function. 9 Kirchhoff. 229 Hysteresis. 54. residual charge of. 291 Hittorf. 292 Hoff. principle of varying action. j Glazebrook. 99 Joule.un LUC clcuiruiuimve iuii*c ui uuiLciica. 72 Hamilton.
Moderncn Theorien der Ckeiirie. 40 thermal effect Mercury vapour. Swing's researches on. 130 Nernst and v. Electricity and Magnetism. 49. 47. 72 arising from the Hall effect. 50 58 effects due to. 98. 115 Pfeffer on osmotic pressure. Sr. ii' Newall. 223 Maximum work. in chemical equilibrium. 116 Neutral gas. 291 Meyer. 225 Natanson. 293 Ohm's Law for electrolytes. 44 due effect of torsion on. 186 of. 225 Meyer. 186 Peltier effect. 192 Muir's Principles of Chemistry. 175 Pfeffer's Osiitotische " Untersuchtmgen. effect of surface tension on the density of salt solutions. 133. and L. 186 Osmosis. 54 Magnetization. 207 Monckmann. discharge of electricity through liquids. 90. Victor. 50 58 change of length due to. 61 strains produced by.. zoo Neesen on residual torsion. 54 effect of strain on. 44. 64 a magnetic field. 67. Berthelot's Law of. Phosphorus pentachloride. 240 Mass. electromotive forces due to flow of hea in a magnetic field. inertia. Ettinghausen. 65 Magnetism. 220 Maxwell. 289 Theory of Heat. effects due to. electric discharge through. E. . 61 to torsion. dissociation " 208 . Lothar. 294 Osmometer.produced by twisting a wire conveying a current. on the dissociation of a solid into two gases. 53. 164 strains produced by an electric field. effect of. 2T2. 74 produced by circularly polarized light. terms in Lagrangian function depending on. 52 on the constitution of bodies. dissociation of nitrogen tetroxide. 103 on chemical action. effects of surface of vessel on dissociation. 134 Mechanical force between circuits conveying currents. 45. 41.
178 the freezing point of solutions. 109. conduction through alloys. 251 Schuster. effect of. 83. i Routh. effect of pressure on. effect of in. 183 gases. diffusion of. 172 Raoult. 269 Riemann. 291 Second Law of Thermodynamics. dissociation of. compressibility of. Schumann. 81 Residual charge of a Leyden jar. 296 Rb'ntgen and Schneider on the compressibility of salt solutions. 83. 87. 182 light in a magnetic field. solutions. electric discharge through mercury vapour. compressibility surface tension of. vsyj strains in a dielectric due to electrification. 10 Rowland. 183 190 . of. 87. 175. 2 1 2 on freezing point. 2 Rayleigh. 128 Resistance. 99 Self induction. 252 pores. 254 Salts. electrical. Lord. 245 surface tension on. 262 pressure on the solubility of. coefficient of. Si Theory of Sound. 46 reciprocal relations. compressibility of salt solutions. 245 Schneider. 136 Residual effects. Si Reciprocal relations. 255 292 255 Solutions. rotation of plane of polarization of Salt solutions. 251 of liquids in fine drops. i surface tension of salt solutions. 289 effect of strain on.v^nuncKe. 40 251 Solubility. effect of dissolved salt on vapour pressure. coefficient of magnetization for small magnetic fore Rain drops. 302 Reversible thermal effects due to a current of electricity. law of force between two moving electrified spheres. Rigid Dynamics. 9 Stability of Motion. 64 effect of pressure on the formation of. 183 surface tension of. 37 RobertsAusten. uibuna.rge ui tuecuiciiy uuuuyn ii^uius. see Rontgen and Schneider.
47 Surface tension of solutions. 227 Thomson. 257 Thomsen. 64 Spheres. produced by communicating a charge of body. 191 freezing point of solutions. 168 chemical equilibrium. 99 coefficient of magnetization. 62 effect on vapour pressure. 109 reversible. 87 vapour pressure. 113 Streintz. force between two moving electrified spheres. 102 electromotive force of batteries. no 113 127 water. Second Law Thermoelectric effects of strain. 162. 163 255 dissociation of gases. 201 Thomson Thermal effects change of. 259 solubility. 99 Thermoelectricity. 190 Surface tension. 65. 262 chemical equilibrium. 105 chemical equilibrium. Thermochemische Untersuclmngen. effect of current on elasticity of wire. 203 density of solutions. 221 dissociation. 18 Temperature. 102 magnetization. 65. effect of temperature on. 234 Tait. effect of on the electromotive force required to decom change of temperature solubility. 101 thermoelectric effects of. absolute. produced by strain. 239 freezing point. 101 due to change of electrification. 251 pose an electrolyte.Specific inductive capacity. So Strain in a dielectric due to electrification. James. 102 strain on. effect of pressure on the freezing point of . 302 clue to. Natural Philosophy. 95 effect on specific inductive capacity. 101 due to a current of electricity. 35 Steady state. 43 Stresses produced by magnetic field. 103 change of strain. Thermodynamics. 237 and. no electricity to a 112 of. 251 electric resistance.
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