UM B I A U N I V E R S I T Y I N

T HE

PU LI C ATI O N N UM

C I TY

B ER

OF N E W

YO R K

T HR E E

H E E R N E S T K E MPT O N AD AM S FUN D FO R PH YS I C AL R E S E AR C H
E ST A

B LISH ED

D E C EM

BER

1 7 T H , 1 90 4

E I G H T LE C T URE S
T H E O R E T I C A L P H Y SI C S
D ELI V ER E D

AT C OLUM B I A U N I V E R S I T Y
I N 1 90 9

BY

M AX

P L AN C K
P R O F E SS O R O F T H E O RET I C A L P H Y SI C S I N T H E U N I V ER SI T Y O F B ER L I N
LE CTU RER I N M A T H EMA T I C A L P H YSI C S I N C O LU M B I A U N I V ER SI T Y F O R 1 9 0 9

TRAN S LA T ED B Y
A P W I LLS
MA TH EM T I C A L P H Y SI C S I N C O LU M I A U N I ER SI T Y
.

P R O F E SS O R

OF

N E W YO R K

C O L UM B I A UN I V E R S I T Y P R E S S
1915

AN LA
S

TE D AN D

PUB L IS H E D

AN

E M EN T W I TH
H I RZ
E L LE I P Z
I G O W NER O F T H E O RI G I N A L C O P YR I GH T
C O PY R I GH T 1 9 1 5 B Y C OLU M B I A UNI V ER S I T Y P RE S S

TR

ARR

BY

PRESS O F
THE NEW E R A P R N TI N G CO MPAN Y
LA N CASTER PA
I

1915

h e s eve ntee nt h d y o f D e c e m b e r n i net ee n h u n d re d a nd f o u r Ed wa d D e

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i t y 1 90 5 6
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1 60 pp
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Ph y i in C l m bi Uni ver it y
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PR E F A C E T O

O R I GI NAL

ED I TI ON

The

present boo k has for its object the pres e ntation o f th e

lectures which I deliver e d a s foreign l e cturer at C olumbia Un i
v e rsity in the spring of the pres e nt year under the t itle
T he
Pr e sent S ystem o f T h e or e tical Physics
T h e points o f view
which inuenced me in the sel e ction an d treatment o f the
material are given at t h e beginning of the rst lecture E ss e n
t i a lly they represent t he extension o f a th e or e tical physical
scheme the fundamental elements of which I develop e d i n an

address at Leyden entitled : Th e Unity of th e Physical C oncept

of the Universe
T herefore I regard it a s advantageous to
consider again some o f the topics o f that lecture T h e presen
t a t i o n will n ot and can n ot of course claim to cover e xh a u s
t iv e ly i n all directions the principles of theoretical physics
T H E A UTH O R

B ER LI N

1 9 09

T R A NS LAT O R S PR EF A C E

At the request of th e Adams Fund Advisory

C ommittee and
with the cons e nt of the a uthor t h e following translatio n of Pro
fe ss o r Planck s C olumbia Lectures was undertak e n I t i s hop e d
that the translation will be of serv i ce to many of those int e r
e st e d i n the developm e nt of theoretical physics who i n spite of
the inevit able l oss prefer a translated t e xt i n E ngl i sh t o an
original text i n G erman S ince the time of the publ i cation of
the original text some of the subjects treat e d particularly that
of heat ra d iation have received much attention with the result
that s ome of the points of view taken at that time have und e r
gon e considerable modications Th e author consid e rs i t d e
sirable however t o have the translati on conform to the original
text since th e n ature an d extent of these mo d ications can
best be appreciated by ref e rence to the recent literature r e lat
ing to the matters in qu e stion
A P WI LLS
,

v ii

C O NTE N T S
F IR ST

L ECTUR E

P AG E

I ntroduction

R eversibility

an d I rrevers i bility

L ECTU R E

S ECOND
T h ermodynamic S tat e s

At o m i c T h e o ry

Ma t t e r

of

of E quil i brium in
TH I RD

L ECTURE

D ilute

L ECTUR E

F OURTH

L ECTU R E

G eneral

D ynamics

E I GHTH

Ge n e ral

D ynamics

70

87

L ECT UR E

Principle of

ix

Least Action

L ECTUR E

Principl e o f

41

S tatistical T heory
S E V ENTH

21

58

E lectrodynamic T heory
S I X TH

H e at R adiation

L ECTU R E

E quation of S tate fo r a M o na t o m i e G as
H e at R adiation

S olut i ons

F I F TH

97

R elativity

1 12

F I RS T LE C T UR E

INT R ODUCT I ON :

R E V ERS I B I L I TY

AND IRREVERS I B I L I TY

cord i al invitation which

the Pr e sident of C olumbia Univ e rsity extended t o me to
deliv e r at this promin e nt cent e r of American sci e nce s ome
l e ctur e s in the domain of theoretical physics h a s inspired in
me a s e nse of the hig h h onor and distinction thus confe rr e d
upon me and i n no l ess degr e e a consciousness of the
special obligations which through its acceptance woul d be
impos e d upon me I f I am t o count upon meeting i n some
measure your j ust exp e ctations I can succ ee d only through
directing your attention t o the branches of my scienc e with
whic h I mys e lf have been specially and d ee ply concern e d thus
exposing mys e lf t o the danger that my report i n certain respects
shall ther e by have s om e wh at too subjective a coloring
From those points of vi e w which app e ar t o me the most
striking it i s my d e sire t o d e pict for you in these l e ct ur e s the
present status of the syst e m of th e or etical physics I d o not
s a y : the pr e sent status of theoretical physics ; for t o cover this
far broader subject ev e n approximately t h e numb e r of l e ctur e
hours at my disposal woul d by n o m e ans sufce T ime limita
tions forbid the ext e nsive consideration of the details of this great
e l d of lear ning ; b ut it will b e quite possible t o d e v e lop for you in
b old outl in e a representation of the syst e m as a whole that is to
give a sk e t c h of the fundamental laws whic h rul e i n the physics
of today O f the most important hypoth e se s empl oyed and O f
the gr e at ideas which have r e cently forc e d thems e lv e s into th e
subject I w i ll oft e n gladly e nd e avor t o go int o details b ut not
in th e s e ns e of a thorough treatm e nt of the subj e ct and only with
the obj e ct of making the general la w s more clear through appro
Co llea gu es , la di es

an

d gentlemen : Th e

F I RST L E CT URE

sp e cially chos e n examples I sh all select th e se examples

from the most var i e d branch e s of physics
I f w e wish to obtain a corr e ct understanding of the achi e v e
m e nts of th e or e t i cal physics we must guard i n e qual m e as u re
against th e mistake of ov e r e stimating th e s e achi e vements and
on the oth e r hand against the corresponding mistake of under
e stimating them T hat t h e second mistak e is ac tually often
made is S hown by the circ u mstanc e that quite r e cently voices
have been loudly raised maintaining the bankruptcy and
d eb ac le of the whole of n atural science
Bu t I thi n k such
assertions may e as i ly be refut e d by ref e r e nce to the simple fact
that with each d e cade the numb e r and th e S ignicance of the
means increas e whereby mankind l e arns directly through th e
aid of theoretical physics to make n ature us e ful for its o wn
purposes Th e technology of today would be impossibl e without
the aid of theor e tical physics Th e development of the whole
of e lectro -t e chnics from galvan oplasty to wir e less telegraphy
is a striking proof of this not to mention a e rial navigation O n
the other hand the mistak e of ov e r e stimating th e achievements
of theoretical ph ysics app e ars to m e to b e much mor e dang e rous
and this danger is particularly thr e at e n e d b v those who have
pen e trated comparativ e ly little into the heart of the subject
T hey maintain that som e time through a proper improve ment
of our scienc e it will be possible not only to represe nt com
l
p e t e ly thro u gh ph y sical formulae th e inn e r constitution of the
atoms bu t also th e laws of mental l i f e I think that there i s
nothing in the world entitling us to the on e or the oth e r of
these expectations O n the other hand I b e li e ve that th e re is
much which d i rectly opposes them Le t us e ndeavor then to
follow the middl e course and not to deviate appreciably toward
the one side or the oth e r
Wh e n we s ee k for a solid immovable foundation which is able
to carry the whol e structur e of theoretical physics w e me e t
w i th the questions : W hat lies at th e bottom of physics ? W hat
is the mat e rial with which it operat e s ? Fortunat e ly there i s
p ri a t e

I N TRODUCT I O N ! R EVERS I B I L I TY AND I RR E V ER S I B ILIT Y

a complete answer t o this qu e stion T h e mat e rial wit h which

th e or e tical phys i cs operat e s is m e asurem e nts and math e matics
is the chi e f tool with wh i ch t h i s mat e rial is work e d All physical
ideas d e p e nd upon m e asur e m e nts more or less exactly carri e d
out and each physical d e nition e ach physical law possesses
a more den i t e S ign i canc e the near e r it can be brought into
accord with the r e sults of measur e m e n t s N ow m e asur e ments
are made with the aid of the s e nses ; b e for e all with that of sight
with h e aring and wit h f e e ling T hus far one can say t h at th e
origin and the foundation of all physical r e s e arch are seated in
our sens e perceptions T hrough sense percept i ons only d o w e
experience anything of nature ; they are the highest court of
appeal in questions under d i spute This vi e w is completely
conrmed by a glance at the historical d eve lopment of physical
science Physics grows upon the ground of sensat i ons The
rst ph y sical ideas derived were from the ind i vidual perceptions
of man and accordingly physics was subdivided int o : physics
of the e ye (optics ) physics of the ear (acoustics ) and physics of
heat sensation (theory of h e at ) I t may well b e said that s o
far as there was a domain of sense s o far extended originally
the domain of physics T herefore it appears that i n the b e
ginning the division o f physics was bas e d upon the pecul i arities
of man I t possess e d in short a n anthropomorphic character
T his appears als o i n that physical research when not occupi e d
with special sense perceptions is concerned with practical lif e
and particularly with t he practical needs of men T hus the
art of geodesy led to g e ometry the study of machinery to m e
and the conclusion l i e s near that physics i n the last
c h a nic s
analysis had only t o do with the sense perceptions and needs
of mankind
I n accordance wit h this v iew the sense perceptions are the
essential elements of the world ; t o construct an object as oppos e d
to sense perceptions is more or l e ss a n arbitrary matt e r of w i ll
I n fact w h en I S peak of a tree I really mean only a compl e x of
sense p e rcept i ons : I can s e e it I can h e ar th e rustling of its
.

F I R S T L E CT URE

branches I can smell its fragrance I e xperience pain if I k n ock

my head against it b ut d i sr e gard i ng all of t h ese sensations
there remains nothing t o b e made the obj ect of a measurement
wh e rewith therefore natural s cience can occupy itself Th is is
certainly true I n accordance wit h this view the problem of
p h ysics consists o nly i n the relating of sense perceptions i n a c
c o rd a n c e wit h experience t o xed laws ; or as one may express
it in the greatest possibl e economic accommodation of our ideas
to our sensati ons a n operation which we undertake solely
because it i s of us e t o us i n the general b attl e of existence
All this appears extraordinarily simple and clear a nd in a c
w i th it the fact may r e adily b e explained that
c o rd a n c e
this positivist V i e w i s quite widely spread i n scientic circles
today I t permits s o far as it is limited t o the standpoint here
d e picted (not always d one consistently by the exponents of
positivism ) n o hypothesis n o metaphysics ; all i s clear and
plain I will go still furth e r ; this conception never leads to an
actual contradiction I may even say it can l ead t o no contra
diction B ut ladies and gentlemen th i s view has never con
tributed t o any advance i n physics I f phys i cs is t o advance in
a c e rtain s e nse its problem must be stated in quite the inverse
way on account of th e fact that this conception is inadequate
and at b ottom possess e s only a formal meaning
T h e proof of the corr e ctness of this assertion is to be found
directly from a consideration of t h e process of developme nt
which theor e tical physics h a s actually undergone and which
one certainly cannot fail t o designate a s essential Le t us
compare the system of physics of today with t h e earl i e r and
more primitive system which I have d e pict e d ab ov e At the
rst glance we encounter the most striking di ff erence of all that
in the present system as well i n the division of the various
physical domains as i n all physical de n itions the h istorical
e lement plays a much small e r r ole than i n the earlier system
While originally as I have S hown above t h e fundamental ideas
of physics were taken from the specic s e nse perceptions of m a n
,

I NTRODUCT I ON : REV ERS I B I L I TY AND

IR R E V E R S I B I LI I Y
'

the latter ar e today i n large m e as u re e xcl u d e d f r o m phy s i cal

acoustics o ptics a nd the th e ory of heat T h e phys i c a l d e
mitions of tone color a nd of t e mp e rature ar e today i n no
wise derived from perception through the correspond i ng senses ;
but tone and col or are d e ned through a vibrat i on numb e r or
wave l e ngth and the t emperat u re through t h e vol ume ch a nge
of a th e rmom e tric substance or through a t e mp e rature scale
bas e d on the second law of thermodynamics ; but h e at s e nsation
is in no wise m e ntioned in connection with th e t e mp e ratur e
With t h e idea o f force it has not b ee n otherwis e W ithout
doubt the word force or i g i nally m e ant bod i ly force corr e spond
ing to t h e circumstance that the oldest tools the ax hamm e r
and mallet were swung by man s hands and that t h e rst
machines the l e ver roller and screw w e r e operated by m e n
or animals This S hows that t h e idea of force was or i ginally
derived from the sense of force or muscular sens e and was
therefore a specic sense perception C ons e quently I r e gard
it today as quite essential in a l e cture o n mechanics t o r e f e r at
any rate i n the i ntroduction t o th e original meaning of th e force
idea B ut i n the modern exact denition of forc e the specic
notion of s e nse perception is eliminated as in the case of color
sense and we may s a y quite in general that i n mod e rn th e or et
ical physics the specic sense perceptions play a much small e r r ele
in all physical denitions than formerly I n f a c t the cro wd ing
into the background of the specic sense el e ments go e s s o far
that the branches of physics which were originally compl e tely
and uniquely characteri z ed by an arrangement i n accordance
with denite sense perc e ptions ha v e fallen apart i n consequ e nce
of the l oosening of the b onds between di ff erent and wid e ly
separated bra n ches on account of the general advance towards
simplication and coordination Th e best example of this is
furnished by the theory of h e at E arli e r h e at form e d a s e pa
rate and unied domain of physics charact e r i z ed through th e
perceptions of h e a t sensation T oday one nds i n wel l nigh all
physics textbooks d e aling with heat a whole d omain that of
,

F IR ST LECTUR E

radiant heat separated and treat e d under optics Th e s ig ni

c a nc e of heat perception no l onger sufces t o bring together
the heterogeneous parts
In short we may s a y that t h e c h aracteristic feature of the entire
previous development of theoretical physics i s a d e nite elimina
tion from all physical ideas of the anthropomorphic elements par
t i c u la rly those of specic sense perceptions
On the other h and
as we h ave seen ab ove if one reects that the perceptions form
the point of departure i n all p h ysical research an d that it is i m
possible t o contemplate th e ir absol ute exclusion because w e can
not c l ose the s ource of all our knowledge then this conscious
departure from the original conceptions must always appear
astonis h ing or even parado x ical T here is scarcely a fact i n the
h istory of physics whic h today s tands out s o clearly as this
N ow what are the great advantages t o b e gained through suc h
W hat is the result for the
a real obliteration of personality ?
sa k e of whose achievement are sacriced the directness and
succinctness suc h a s only the special sense percepti ons vouchsafe
to physical ideas ?
T he result i s nothing more than the attainment of unity
and compactness i n our system of theoretical p h ysics and in
fact the unity of the system not o nly i n relation t o all of its
details but also in relation t o physicists of all places all times
all peopl e s all cultures C ertainly the system of th e oretical
physics shoul d b e adequate not only for the inhabitants of this
earth but also for the i nhabitants of other heavenly bodies
Wh ether the i nhabitants of M ars i n case suc h a ctually exist
~

a
r
s
h ave eyes and c
like our own we d o not know it i s quite
improbable ; but that th e y i n s o far as th e y possess t h e necessary
intelligence recogni z e the law of gravitation and the principle of
energy most physicists woul d hol d a s self evident : a nd anyone
to whom this is not evident had b e tt e r not appeal t o the physicists
for it will always remain for him a n unsolvabl e riddle that the
sam e physics i s made i n th e United States as i n G ermany
T o s u m up we may say that the characteristic f e ature of the
.

I N T RODU C T I ON : REVERS I B I L I TY AN D I R R E V E R S I B I LIT Y

actual d e velopm e nt of the syst e m of t h eoret i cal phy s i cs is an

ever ext ending emancipation from the anthropomorphic e l e m e nts
whic h has for its O bject the most compl ete separation po s sible
of t h e syst e m of physics and the individual pers onality of the
physicist O ne may call this the O bjectiven e ss of the system
of physics I n ord e r t o exclud e the possibility of any m is u nd e r
standing I wish t o emphasize pa rticularly that we have here
to do not with an absolute separation of phys i cs from the

physicis t for a physics without the physicist is unthinkable

but wit h the elimination of th e indi v iduality of the particular
physicist and th e refore with the production of a common system
of physics for all physicists
N ow h o w does this pr i nciple agree wit h the positi v ist con
S eparation of the system of physics
c e p t i o ns mentioned above ?
from the individual personality of the physic i st ? Opposed to
this principle in accordance with those conceptions each
particular ph ysicist must have h is special system of physics in
case that complete elimination of all metaphysical elements is
e ff ected ; for physics occupies itself only with the facts discovered
throug h perceptions and only the individual perceptions are
directly involv e d T hat other living beings have sensations is
strictly S peaking but a v e ry probable though arb i trary conclusion
from analogy T h e syst e m of physics i s th e refore primarily a n
individual matter and if t w o physicist s acc e pt th e sam e syst e m
it i s a very happy circumstance i n connection with their personal
r e latio n ship b ut it i s not essentially necessary One can r e gard
this view -point however he will ; in physics it is certainly quite
fruitl e ss a nd this i s all that I care t o maintain here C ertainly
I might add eac h great physical id e a m e ans a furth e r advance
toward the emancipation from anthropomorphic ideas T his
was true i n the passage from the Ptol e maic t o the C op e rnican
cosmical syst e m j ust a s it is true at the pr e s e nt tim e for the
apparently imp e nding passage from the S O-called classical m e
c h a n i c s of mass points t o the g e neral dynam i cs originat i ng i n
the principl e of relativity I n accordance with this man and
,

F I R S T L E CT URE

th e earth upon which he dwells are removed from the centre

of t h e world I t may be predict e d that in this c e ntury the
id e a of time will be div e sted of the absolute charact e r with
whic h men have been accustom e d t o endow it (cf the nal
lecture) C ertainly the sacrices demanded by every such
revolution in the intuitive point of view are enormous ; c o nse
quently the resistance against suc h a change i s very great B ut
the d evel opment of sci e nce i s n ot t o b e permanently h alted
thereby ; o n the c ontrary its strongest impetus is e x perienced
throug h precis e ly those forc e s which attain success in the strug
gle against the ol d p oints of view a nd t o this e xtent suc h a
struggle is constantly necessary and useful
N ow how far h ave we advanc e d t oday t oward the unicati on
of our system of physics ? T he n umerous independent domains
of the earlier physics now appear reduced t o two ; mechanics and
electrodynamics or a s one may s a y : the physics of material
bodies and the physics of the ether T he former compr eh en d s
acoustics phenomena i n material b odies and chemical phenom
ena ; t h e latter magnetism optics and radiant h eat B ut is
this division a fundamental on e ? W ill it prove nal ? T his
is a question of gre at cons e quence for the future devel opment of
physics For myself I believe it must b e a nswered in the
negative and upon the following grounds : mechanics and electro
dynamics cannot b e permanently sharply di ff e rentiated from
eac h other D oes the process of light emission for example
belong t o mechanics or t o electrodynamics ? T o w h ic h domain
shall b e assign e d the laws of motion of electrons ? At rst
glance one may perhaps s a y : t o electrodynamics since with
the electrons ponderable matt e r does not play any r le B ut
let one direct h i s att e ntion t o the motion of free electrons in
metals Th ere h e will nd in the study of the classical re
searches o f H A Lorentz for exampl e that the laws obey e d by
the electrons belong rat h er t o the kinetic the ory of gases th an
to electrodynamics I n general it app e ars to me that the
original differ e nc e s between proc e sses in the eth e r and processes
.

I N T RODU CTI ON : R E V ERS I B I L I TY AND I RR E V ER S I B ILIT Y

in material bodies are t o b e considered as disappearing E lectro

dynamics and mechanics are not s o remarkably far apart as is
considered to b e the case by many people who already sp e ak of a
conict bet w een the mechanical and the electrodynamic vi ew s
of the world M echanics requires for its foundation essent i ally
nothing more than the ideas of S pace of tim e and of that which
is moving wh e ther one consid e rs this a s a substance or a state
Th e same ideas are als o i nvolv e d in electrodynamics
A suffi
c i e n t ly generali z ed conception of mechanics can therefor e also
well include electrodynamics and i n fact th e r e ar e many indica
tions pointing t oward the ultimate amalgamation of these two
subj ects the d o m a i ns o f which already overlap in some measure
I f therefore the gulf between eth e r and matter be once bridg e d
what i s the point of vi e w which in the last analysis w i ll best
serve i n the subdivision of the system of physics ? Th e answ e r
t o th is question will characterize the whole nature of the furth e r
development of our science It is therefore the most important
among a ll t h ose w h ic h I propose t o treat today B u t for th e
purposes of a closer investigation it is necessary that we go som e
what more deeply into the peculiarities of physical principles
We shall best begin at that point from whic h the rst step was
made toward the a ctual reali z ation of the uni e d syst e m of
p h ysics previously postulated by t h e philosoph e rs only ; at the
principle of conservation of energy For the idea of energy is
the only one besides those of space and time which is common to
all t h e various domains of physics In accordance wit h what I
have stated ab ove it will b e apparent and quite self e vident to
you that the principle of energy before its general formulari z ation
by M ayer J oule and H e lmholz als o b ore an anthropomorphic
character The roots of this principle lay alr e ady i n the recog
nit i o n of the fact that no one i s able t o obtain useful work from
nothing ; and this recognition had originated ess e ntially i n th e
exp e riences whic h were gather e d i n att e mpts at the solution of a
technical probl e m : the discov e ry of p e rpetual motion T o this
extent perpetual motio n h as com e t o have for physics a far
.

F I RST LECTUR E

10

r e aching S ignicance similar t o that of alch e my for the chemist

although it was n ot the positi v e b ut rather t h e n e gative r e sults
exp e r i m e nts through which science was ad v anc e d
O f these
T oday w e sp e ak of the principle of energy quite without r e f e r e nce
to the technical viewpoint or t o that of man We sa y that the
total amount of energy of an isolated syst e m of bodies is a
quantity whose amount can b e neither increased nor diminished
through any kind of process with in the system and we no l onger
consider the accuracy wit h which this law holds a s depend e nt
upon the ren ement of the methods which we at present possess
of testing experimentally the question of the reali z ation of
perpetual motion I n this strictly speaking unprovable general
i z a t i o n impressed upon us with elemental force lies the eman
c ip a t i o n from the a nthropomorphic elements mentioned ab ove
Wh ile the principl e of energy stands before us as a complete
independent structure freed from and independent of the acci
dents appertaining t o its historical development this is by no
means tr u e i n equal measure in the case of that principle w h ich
R C lausius introduced into physics ; namely the second law
of t h ermody nam i cs T his law plays a very peculiar rOle in the
development of physical science t o the extent that one is not
able t o assert today that for it a generally recogniz e d , and there
fore obj ective formularization has been found I n our present
Consideration it is therefore a matter of particular interest to
e x amine more closely its signicance
I n contrast t o the rst law of thermodynamics or the energy
principle the second l aw may be characteri z ed as follows While
the rst la w permits in all processes of nature neither the creation
nor destruction of en e rgy but permits of transformations only
the second law goes still further into the limitation of the p o s
sible processes of nature in that it permits not all kinds of trans
formations but only c e rtain types subj ect t o cert ain con
Th e second la w occup i es itself therefore with the
d it i o ns
qu e stion of th e kind and in particular wit h t h e direction of any
natural process
,

I NTRODUCT I ON : REVERS I B I L I TY

I RREVERS I B I L I TY

AN D

At

11

this point a mistak e has frequently b ee n mad e w hich has

h i ndered i n a very pronounc e d mann e r th e ad v ance o f sc i ence
up to t he pr e s e nt day I n t h e end e avor to give t o th e s e cond
law of thermodynamics th e most g e n e ral charact e r possible it
has been proclaim e d by followers of W O st w al d as the s e c o nd
law of energetics a nd the att e mpt made s o t o formulat e it that
it shall d e t e rmine quite g e n e rally the dir e ction of every process
occurring i n nature S ome weeks ago I r e ad i n a p u blic academic
address of a n esteemed colleague th e statement that the import
of the s e cond law consists i n this that a stone falls do w nwards
that water ows not up hill but down that e lectricity o w s from
a higher t o a l ower potential and s o on This is a mistake whic h
at present is altogether too prevalent not to warrant mention
h ere
Th e trut h i s t h ese statements are false
A stone can j ust as
well rise i n the air as fall downwards ; wat e r can l i kewise ow u p
wards a s for example in a spring ; electricity can ow very well
from a l ower t o a higher pot e ntial as i n th e ease of oscillating dis
charge o f a condenser Th e statements are O bviously quite cor
rect if one applies them to a stone originally at rest t o water at
rest t o electricity at rest ; but then they follow immediately from
the energy principle and one does not need to add a special s e cond
law For i n accordance with the energy principl e the k inetic
energy of the stone or of the water can only originate at the
cost of gravitational energy i e the center of mass must descend
I f therefore motion is t o take place at all it i s necessary
T hat is the
that the gravitational energy s h all d e crease
center of mass must descend I n like manner an el e ctric cur
rent between two condenser plates can originate only at the
cost of electrical energy already pres e nt ; the el e ctricity must
th e r e fore pass t o a l ow e r pot e ntial
I f however motion and
current be alr e ady pr e s e nt th e n on e is not abl e t o s a y a priori
anything i n r e gard t o the d i r e ction of the chang e ; it can take
plac e ust as w e ll i n o ne dir e ction a s th e o th e r T h e r e for e th e r e
is no n e w insight into nature t o b e O bt a in e d from this point o f
vi ew
,

F I RST LECTUR E

12

Upon an equally inadequate basis rests another conception of

the second law which I shall now mention I n considering the cir
c u m st a nc e t h at mechanical work may very easily b e transformed
into h eat as by friction while on the other hand heat can only
wit h di fficulty b e transformed into work the attempt has b ee n
made so t o characteri z e the second law t h at i n nature t h e trans
formation of wor k int o h eat can take place completely while
that of heat into work on the other hand only i ncompletely and
in suc h manner that every time a quantity of heat i s transformed
int o wor k another corresponding q uantity of energy must n e c e s
s a rily undergo at the same time a compensating transforma
tion a s e g t h e passage of heat from a h igher t o a lower
temperature Thi s assertion i s in certain special cases correct
but does not strike i n general at the true I mport of the matter
as I shall S how by a simple example
One of t h e most important laws of thermodynamics is t h at
t h e total energy of an ideal gas depends only upon its tempera;
ture a nd not upon its volume I f a n ideal gas be allowed to
expand w h ile doing work and if the cooling of t h e gas be prevented
t h rough the simultaneous ad d ition of h eat from a heat reservoir
at h igher temperature t h e gas remains unchanged i n temperature
and energy content and one may s a y that t h e heat furnished
by the h eat reservoir is completely transformed into work without
exchange of energy N ot the least objection can be urged
against this assertion Th e law of i ncomplete transformation
of heat int o wor k is retained only throug h the adoption of a
different point of view but which h as nothing t o d o wit h the
status of the physical facts a nd only modies the way of l oo k ing
at the matter a nd therefore can neither b e supported nor con
t ra di c t e d throug h facts ; namely throug h the introduction ad hoc
of new particular kinds of energy in that one divides the energy
of the gas int o numerous parts whic h individually can depend
upon the volume B ut it is a priori evident t h at one can never
derive from so articial a denition a new physical law and it is
with suc h that w e have t o d o when we pass from the rst law
the principle of c onservatio n of e n e rgy t o t h e second law
.

I N T RODU CTI ON : REVERS I B I LI TY AND I RR E V ER S I B ILIT Y

I desire no w t o introduce such a new physical la w : I t i s not

possible to construct a p e riod i cally funct i on i ng m o tor w h i ch in
principle does not involv e more than th e raising of a l oad and the
cooling of a heat r e servoir
I t is t o be understood that i n one
cycl e of the motor quite arbitrary compl i c a t e d processes may
tak e plac e but that a ft e r t h e completion of on e cycl
e
th
e
re
S
hall

remain no oth e r changes i n the surroundings than that the heat

r e servoir is cooled and that the load is raised a corr e sponding
distanc e which may b e calculated from the rst law S uc h a
motor could of course b e used at the same time as a refrigerating
machine also without any further exp e nditure of energy and
mat e rials S uch a motor would moreover be the most effi ci e nt
i n the world since it would involve n o cost t o run it ; for th e
eart h the atmosphere or the ocean could be utiliz e d a st h e heat
reservoir We S hall call this i n accordance with the proposal of
W Ostwald perpetual motion of the S econd kind Wh e ther in
nature such a motion is actually possibl e cannot be inferred from
and
may
only
be
d
e
termin
e
d
by
special
e rgy principle
M
exper i me nts
J ust as the impossibility of perpetual motion of th e rst kind
l e ad s t o the principle of the conservation of e nergy the quite
i nd e p e nd e nt principle of th e impossibility of perpetual motion of
the second kind l e ads to the second law of thermodynami cs
and if we assume this impossibility as proven experimentally
the general law follows immediately : the re a re p roc es s es i n

n a tu re

whi c h i n

no

p oss i ble wa y

c an

be m a de

c o mp lete ly reve rs i

For consider e g a frictional process through which m e

c h a ni c a l work i s transformed into heat with the aid of suitable
apparatus if it w e re actually possible t o make i n s ome way such
complicated apparatus completely rev e rsible s o that ev e rywhere
in nature exactly the same conditions be r ee stablish e d as existed
at the beginning of the frictional proc e ss then the apparatus
consid e r e d woul d b e nothing more than the motor described
abov e furnishing a p e rp e tual motion of the s e cond kind T his
appears evident imm e d i at e ly if one clearly perc e ives what th e

ble

F IR ST LECTURE

14

apparatus would accomplish : transformati on of heat int o work

w i th out any further outstanding change
We call such a proc e ss which i n n o wise can b e made completely
reversible an irreversibl e process and all other processes re
v e rs ib le process e s ; an d thus we strike the kernel of the second
law of th ermodynamics when we sa y that irreversible processes
occur in nature I n accordance with this the changes i n nature
have a unidirectional tendency W it h eac h i rreversible process
the world takes a st e p forward the trace s of which under no
circumstances can b e completely obliterated B esides friction
examples of irreversibl e processes are : heat conduction diffusion
conduction of electricity i n c onduct ors of nite resistance
emission of light and heat radiation disintegratio n of t h e atom
in radioactive substance s a nd s o on On the other hand ex
amples of reversible processes are : motion of the planets free
fall i n empty space t h e undamped m oti on of a pendulum
the fricti onles s o w of liquids the propagation of lig h t and
sound waves without absorption and refraction undamped
electrical vibrations and s o on For all thes e processes a re
already periodic or may b e made completely reversible t h rough
suitable contrivances s o that there remains n o outstanding
change i n natur e ; for example the free fall of a b ody whereby
the a cqu ir ed v e locity i s utilized t o raise the b ody a gain t o its
original h e ight ; a light or s ound wave which i s allowed in a suitable
manner t o b e t otally reected from a perfect mirror
What now are the general properties and criteria of irreversible
processes and what i s the g e neral quantitative measure of
irreversibility ? This qu e stion has be e n examin e d and answered
in the most wid e ly differ e nt ways a nd it i s evident here again
how di ffi cult it i s t o reach a correct formulari z ation of a prob
lem J ust a s originally we came upon the trail of the energy
principle through the technical probl e m of p e rpetual motion s o
again a technical problem namely that of the steam engine
led t o the differentiation b e t we en r e versible and irreversible
process e s Long ago S adi C arnot recogni z ed although he util
.

I N T RODU CTI ON : REVERS I B I L I TY AND I R RE V ER S I B ILI T Y

iz e d

an incorrect conc e ption of the natur e of h e at that irre

v e rs i b le proc e ss e s ar e l e ss e conom i cal than revers i ble or that i n
an irre v ersible proc e ss a certain opportun i ty to d e r i ve m e chan
ical work from h e at is lost W hat th e n could have been
S impler than the thought of making qu i t e in gen e ral the meas
ure of the irrev e rsibilit y of a process the quantity of m echanical
work wh i ch i s unavoidably l ost i n the process For a r e v e rsible
process th e n the u navo i dably lost work i s naturally to be s et
equal t o zero T his view i n accordance with which the imp o rt
of t h e second law consists i n a dissipation of useful en e rgy has
in fact i n certain special cases e g i n isoth e rmal processes
proved itself useful I t has persisted th e refore i n c e rtain of
its a spects up t o the present day ; but for the gen e ral case h o w
ever it has shown its e lf as fruitless and i n fact misl e ad i ng T h e
reason for this lies in the fact that the question conc e rn i ng the
lost wor k i n a given irreversible proc e ss i s by no m e a n s t o b e
answered in a determinate mann e r s o l ong as noth i ng further is
specied with regard t o the s ource of energy from w h ich th e work
considered shall b e obtained
H eat conduction is an
An example will make this clear
irreversible process or a s C lausius expresses it : H e at cannot
without compensation pas s from a colder t o a warmer b ody
Wh at now i s t h e work which i n accordance with d e nition is
lost when the quantity of h e at Q passes through dir e ct conduction
from a warmer body a t the temperature TI t o a cold e r b ody at
the temperature T2 ? In ord e r t o answer this question we make
use O f the h eat transf e r involv e d i n carrying out a reversible
C arnot cyclical process b e t w een the two bodies e mploy e d as
h eat reservoirs I n this process a certain amount of work
would b e obtained and it i s just the amount s ought since it is
that which would be l ost in the direct passage by conduction ;
but this has n o d e nite value s o l ong as we d o not know wh e nce
the wor k originates wheth e r e g i n the warmer body or i n th e
colder b ody or from s om e wh e r e e ls e Le t one reect that the
h e at giv e n up by the warm e r body in th e r e v e rs i bl e process is cer
,

F IRS T LECTURE

16

not equal t o the heat absorbed by th e colder body because

a c e rtain amount of h e at is transform e d into work and that we
can identify wit h exactly the same right the quant i ty of heat Q
transferred by the direct process of conduction with that which in
the cyclical process is given up by the warm e r b ody or with that
absorbed by the colder body AS one does the former or the latter
he accordingly obtains for the quantity of lost work in t h e process
of conduction :

t a i nly

Q
We

Tl
T2

T1

or

TI

T2

T2

therefore that the proposed met h od of e xpressing mathe

m a t i c a lly the irreversibility of a process does not i n general effect
its obj ect and at the same time we recognize the peculiar reason
which prevents its d oing s o T he statement of the question is
too anthropomorphic I t i s primarily t oo much concerned with
the needs of mankind i n that it refers directly t o the acqui rement
of useful work
If one require from nature a determinate
answer he must take a more general p oint of view more d i si n
t e re st e d less economic
We shall now seek t o d o this
T his
Le t us consid e r any typical proc e ss occ u rring i n nature
will carry all bodies concerned i n it from a determinate initial
state which I designate as state A int o a determinate n al
state B Th e process is either reversible or irreversible A
third possibility i s excluded B ut whether it is reversible or
irreversible depends s ol e ly upon the nature of the two states A
and B and not at all upon the way i n which t h e process has b een
carried out ; for we are only concerned with the answer to the
question as t o whether or not when the state B i s once reached a
complete return t o A in any conceivable manner may b e a c
complished I f now the complete return from B to A i s not
possible and the process therefore irreversible it is obvious that
the state B may b e distinguished i n nature throug h a certain
property from state A S everal y e ars ago I ventured t o express

this as follows : that nature possesses a greater preference for

state B than for state A I n accordance with this mode O f
se e ,

I N T RODU CTI O N : R E V ERS I B I L I TY AND I R R E V E R S I B I L I TY

expression all those proc e sses of nature ar e imposs i bl e for w hose

nal state natur e poss e ss e s a small e r preference than for the
original state R e versible process e s const i tute a limiting case ;
for such nature possesses an equal prefer e nce for the in i tial and
for the nal state and th e passage between them takes place as
well i n one direction a s the other
W e have now t o see k a physical quantity whose magnitude
S hall serve as a general measure of the preference of nature for
a giv e n state T his quantity must b e one whic h i s directly
determined by the state of the system considered wit h out
reference to the previous history of the system as is the case wit h
the energy wit h the volume and wit h other properti e s of the
system It shoul d possess the peculiarity of increasing in all
irreversible processes and of remaining unchang e d in all revers
ible processes a nd the amount of change which it experienc e s
in a process would furnish a general measure for the irre
v e rs ib ilit y of the process
R
C lausius actually found this quantity and called it
entropy
E very system of bodies possesses in each of its
states a denite entropy and this entropy express e s the pref
erence of nature for the state i n question I t can in all the
processes which take place within the system only increase and
never decrease I f it be desired to consider a process i n w hich
external actions upon the system are present it i s necessary
to consider those b odies in whic h these a ctions originate as
constituting part of the system ; then the law as stated i n the
above form is valid I n accordance wit h it the entropy of a
system of b odies i s simply equal t o the sum of the entropies of
the individual b odies and the entropy of a single body is in
accordance wit h C lausius found by the aid of a certain re
C onduction of heat to a body increases its
v e rsible process
entropy and in fact by a n amount equal to the ratio of the
quant ity of h e at given the body to its temperature S imple
compression on the other hand does not change the entropy
R eturning to th e example m e ntioned above in whic h the
,

F IR ST LECTUR E

18

qua ntity of heat Q is conducted from a warmer body at the

temperature TI t o a colder body at t h e temperature T2 i n
accordance with what prec e des the entropy of the warmer body
d e creases i n this process while o n t h e other h and that of the
cold e r incr e ases and the sum of b oth changes that i s the change
of the total entropy of bot h b odies is :
,

fn

Tl
T his

> o

positiv e quantity furnishes in a manner free from all

arbitrary assumptions the measure of the irreversibility of the
process of heat conduction S uch examples may be cited
indenitely E very chemical process furnishes an increase of
entropy
W e shall here consider only the most general case treated by
C lausius : a n arbitrary reversible or irrevers i ble cyclical process
carried o ut with a ny physico -chemical arrangement utilizing
an arbitrary numb e r of heat reservoirs S ince the arrangement
at the conclusion of the cyclical process is the same a s that at
the beginning the nal stat e of the process is to be distinguished
from the initial state s ol e ly through the different h eat content
of the heat reservoirs and in that a certain amount of mechanical
work has b een furnished or consumed Le t Q b e the h eat given
up in the course of the process by a heat reservoir at the tem
p e ra t u re T and l e t A b e the total work yielded (consisting
e g i n the raising of weights ) ; th e n in accordance with the rst
law of thermodynamics :
2Q
A
,

su m of the changes in
I n accordance with the second
entropy of all t h e heat reservoirs is positiv e or zero I t follows
therefor e since the entropy of a reservoir i s decreased by the
amount (2/ T through th e l oss of heat Q that :
.

Q
<
E
Z
T

T his

is the w ell -known inequality of C lausius

I NTRODUCT I ON : REVERS I B I L I TY

I RREVERS I B I L I TY

AN D

19

I n an isothermal cycl i cal proc e ss T is th e same for all r e servoirs

T herefore :
2 62 E 0
henc e : A E 0
,

T hat

is : i n an isoth e rmal cyclical process h e at is produced and

work i s consum e d I n the limit i ng case a reversibl e isoth e rmal
cyclical process the S ign of equality holds and th e refore the
work consum e d is zero and also the h e at produced Th i s law
plays a l e ading rOIe i n the application of thermodynamics to
physical chemistry
Th e s e cond law of th e rmodynamics including all of its con
sequenc e s has thus led t o the principle of i ncrease o f entropy
Yo u will now readily understand h aving regard t o the questions
mentioned ab ove why I express it as my opinion that i n the
theoretical physics o f the future the rst and most important
differentiation of a ll physical processes will be into reversible
and i rrev e rsible processes
I n fact all reversible processes whether they take place in
material b odies i n the e ther or in both together S how a much
greater similarity among themselves than t o any irreversibl e
process I n the d i fferential equations of reversible processes
the time differential ent e rs only a s a n even pow e r corres
ponding to the circumstance that the S ign of time can be
reversed This holds equally w e ll for vibrations of the p e n
dulum electrical vibrations acoustic and optical waves and
for motions of mass points or of electrons if we only e x
ev e ry kind of damping Bu t t o such processes also
e lude
belong those innitely S low proc e ss e s of th e rmodynamics which
consist of states of equilibrium i n whic h the tim e i n general
plays no rOle or a s one may also say occurs with the z e ro pow e r
which is t o be reckoned as a n ev e n power As H elmholtz has
pointed out all these r e versible processes h ave the common
property that th e y may be compl e tely repres e nted by the principle
of least action w h ich giv e s a denite answ e r t o al l questions con
cerning any such measurable process and t o this extent the
ory of r e v e rsible proc e ss e s may b e r e gard e d as compl e tely estab
li sh e d R eversibl e processes hav e however the disadvantag e that
,

F IRS T LECTURE

20

singly and collectively they are only ideal : i n actual nature there
is no such thing as a r e versible process E very natural proc e ss
involv e s i n greater or les s d e gree friction or conduction of h eat
B u t in the domain of irreversible processes the principle of least
action is n o l onger sufcient ; for the principle of increase of
entropy brings into the system of physics a wholly new element
foreign to the action principle and which demands special
mathematical treatment The unidirectional course of a process
in the attainm e nt of a xed nal state i s related t o it
I hope the f Ore g o i 1 g considerations have su fced t o make clear
to you that t h e d istinction betwe e n reversible and irreversible
processes i s much broader than that between mechanical and
electrical processes and that th e refore this difference wit h better
rig h t than any other may b e taken advantag e of i n classifyi n g
all p h ysical processes and that it may eventually play in the
theoretical physics of the future the principal rOle
However the classication men t ioned is i n n e ed of quite an
essential improvement for it cannot b e denied t h at in t h e form
the system of physics i s still suffering from a strong
se t forth
dose of anthropomorphism I n the den i tion of irreversibility
as well as i n that of entropy reference i s made t o the possibility
of carrying out i n nature certain changes and this means funda
mentally not h ing more than that the division of physical proc
esses i s made dependent upon the manipulative skill of man i n
the art of experimentation whic h c e rtainly d oes not always
remain at a xed stage but is continually b e ing more and more
perfected I f therefore the distinction between reversible a nd
irreversible processes i s actually t o h ave a lasting signicance
for all times it must b e essentially broadened and made inde
pendent o f any reference t o the capacities of mankind H o w this
may happen I desire t o st a t e o ne week from t omorrow T he
lecture of tomorrow will b e devoted t o the problem of bringing
before you s ome of the most important of the great number of
practical consequences following from the entropy principle
.

'

S E C ON D

L E C T UR E

O F E QU I L I B RI UM
S OLUT I ON S

T HE R MODYNAM I C S TATE S

D I LUTE

IN

I n t h e lecture of yesterday I sought to make clear the fact

that the essential and therefore the nal division of all process es
occurring i n natur e is into reversible and irreversible processes
and the characteristic difference betwe e n these two ki nds of
processes a s I h ave further separated them i s that i n irr e v e rsible
processes the entropy increases while i n all r e versible processes
it remains constant T oday I am constrained to S peak of some
of the consequences of this law whic h will illustrat e its ric h fruit
fulness T hey h ave t o do wit h the question of the laws of ther
S ince in nature the entropy can only
m o dyn a m i c equilibrium
increase it follows that the state of a physical conguration
whic h i s completely isolat e d a nd i n which the entropy of
t h e system possesses an absolute maximum is necessarily a
state of stable equilibrium S ince for it no further change is
possible H o w deeply this law underlies a ll p h ysical a nd chem
ical relations has been shown by no one better a nd more com
than
by
ohn
W
illard
G
ibbs
whose
name
not
only
in
J
l
l
e
t
e
y
p
America but i n t h e whole worl d will be counted among those of
t h e most famous theoretical physicists of all times ; to whom to
my sorrow it is no l onger possible for me to tender personally
my r e spects I t would b e gratuitous for me here i n the land
of hi s activity to expatiate fully on the progress of h is ideas
but you will perhaps permit me t o speak in the lecture of to
day o f some of the important applications in which thermo
d ynamic res e arch based on G ibbs works can b e advanced b e
yond his results
T hese applications ref e r to the theory of dilut e solutions and
,

21

SECOND LECTURE

22

w e S hall occupy o urselves today with th e s e whil e I show you

by a d e nite exampl e what fruitfulness is inh e rent in thermo
dynamic th e ory I shall rst characteri z e the probl e m quit e
g e n e rally It h as t o d o with the state of equilibrium of a material
syst e m of any number of arbitrary constituents i n a n arbi
t ra ry n u mber O f phas e s at a given temperature T an d given
pressure p I f the system i s complet e ly i solated and there
fore guard e d against all e xternal th e rmal and m e chanical
actions then in any e nsuing ch ange the entropy of the system will
increase :
,

dS > 0

B ut if as we assume the system sta nds i n suc h relation t o

its surroundings that in any change w h ich the system under
goes the temperat u re T and t h e pressure p are maintained
constant as for i nstance through its introduction into a c alo ri m
eter of great heat capacity and throug h loading with a piston
of xed weight the inequality would suffer a change th e reby
W e must then take account of the fact that the surrounding
bodies also e g the calorimetric liquid will b e involv e d i n the
change I f we d e note t h e entropy of the surrounding b odies by
S o then the following more g e neral equation h olds :
,

dS

dS o

I n this equation

ds o

if Q denote the heat which i s given up in the change by the

surroundings t o the system O n the other hand if U de
note the energy V the volume of the syst e m then in accord
ance wit h the rst law of thermodynamics
,

dU

p dV

C ons e qu e ntly through substitut i on :

,

dS

dU

p dV

> 0

THERM O DYN A M I C STATES O F EQU I L I BR I UM

or s i nc e
,

and

2
.

ar e const a nt :

(1 + p l
T

I f th e r e fore w e put :
,

U+ N

'

(1 )

th e n

M)

0,

and we ha v e the gen e ral law that i n e v e r y isothermal-isobari c

const p
const ) change of state of a phys i cal syst e m
(T
the quantity CI> incr e as e s T h e absolut e ly stable state O f
equilibrium of the system is therefore ch a racteri z ed through
the maxi mum of cI) :
,

54>

(2)

I f the system consist of numerous phases then because CID in

accordance wit h
i s linear a nd homogeneous in S U a nd V
the quantity (I) r e ferring t o the whol e system is the s u m of the
quantities CID referring t o the individual phases I f the expression
for (I) i s known a s a function of the i ndependent variables for
each phas e of the system th e n from equation
all ques
tions concerni ng the con di tions of stabl e equili brium may be
answered N ow withi n limi ts thi s is th e case for dilute solutions

By s olution i n thermodyn ami cs i s m e ant each h omogeneous

phase i n whatever state of aggregation whi ch is compos e d of a
series of di ff erent molecul ar complexes each of w hi ch is rep
resented by a d e nite molecular number I f the molecular
number of a given comple x is great wit h r e ference to a ll the
remaini ng complex e s t h en the solution is called dil ute and the
molecular complex i n question i s called the solvent ; the rema i n
i ng complexes a re call ed the di ssolved substances
Le t us now consid e r a d i lut e s olution w hose state i s determi n e d
by the pressure p the temperatur e T a nd th e molecul ar numb e rs
wh e r e in th e subscript z e ro refers t o the sol v ent
n o n 1 n 2 n3
are all small with respect t o n o
T hen the numb e rs n 1 n2 na
,

24

S ECOND LECTUR E

and on this account the volume V a nd the energy U are linear

functions of the molecular numbers :

U=

n ovo

n10 1

n ou o

n1 u 1

n 20 2

'

n 2u 2

w h erein the o s and a s depend upon p and

From the general equation of entropy :
dU

only

p dV
Q

in which the differentials depend only upon c h anges i n p a nd

and not in the molecular numbers there results therefore :

T,

and from this it follows that the e xpressions multiplied by no n 1

o
dependent upon p and T only are complete di ff erentials
W e may therefore write :
,

p doo

du o
T

du l

( 8 01

p dc l

dn ,

(3)

and by integration obtain :

"

-0

Th e

constant C of integration does not depend upon p and T

but may dep end upon the molecular numbers no n 1
I n ord e r t o e xpress this dependence generally it suffices t o k now
it for a special case for xed values of p and T N o w every
solution passes through appropriate increase of temperature and
decrease of pressure int o the state of a mixture of ideal gases
and for t h is case the entropy is fully k nown the integration
constant b e ing in accordance with G ibbs :
,

'

C =

wh erein

denotes the absolute gas constant and

c o,

cl,

0 2,

T HER M ODYNA MIC S TATE S

E Q U ILI BR I U M

OF

denote the molecular conc e ntrations

7t o

71 i

Co

01

C onsequ e ntly quite in general the entropy of a d i lute solution is :

,

R lo g

n0 s o

R lo g

n1 s 1

co

cl

and nally from this it follows by substitution in e quation (1 )

that :
(I)
n o(g0 0
R l og c o)
n 1 (go 1
R log c l )
(4 )
,

if we put for brevity :

o

u0

so

p v0
,

s0 1

u1
81

(5 )

all of whic h quantities depend only upon p and T

W it h the aid of the expression obtained for (I) we are enabl e d
through equation (2) to answer the qu e stion with r e gard to
thermodynamic equilibrium W e shall rst nd the general
law of equilibrium and then apply it to a seri e s of particularly
interesting special cases
E very material syste m consisting of an arbitrary number of
homogeneous phases may be represented symbolically in th e
following way :
.

n omo)

n l ml ,

no

mo ,

nl

ml

no

mo

nl

H e re

ml

n
,

the molecular numbers are denot e d by n the molecular

weights by m and the individual phas e s are separated from one
another by vertical lines We shall no w suppose that each
phase repr e sents a dilute solution This will be t h e case w h en
each phase contains only a single molecular comple x and t h er e
fore represents a n absolut e ly pure substance ; for then the con
c e nt ra t i o ns of all t h e dissolved substances will be zero
I f now an isobaric-isot h ermal change in the system of such
k ind is possible t h at the molecular numbers
,

n o,

I
0

II

I
o

N
o

SEC OND LECTUR E

26

change S imultan e o u sly by the amounts

572 0 , 072 1 , 571 2 ,

th e n i n accordance with equation

e q u ili b ri u m o b t a i ns with
r e sp e ct t o the occurr e nce of this chang e if when T and p are h e ld
constant the function

is a maximum or in accordanc e with equation

,

(m

R lo g

) 5no

(p 1

co

l og

cl

) 5n 1

(the summation 2 b e i ng extended over all phas e s of the system )

S inc e we are only conc e rned in this equation wit h the ratios of

the

Bn

we put

s,

6no : 5n 1

'

2 V1

wher e in we are to understand by the simultaneously changing

v s i n the variation consid e r e d s i mpl e int e g e r positi v e or negati v e
numbers according as th e mol e cular complex und e r consider
ation is formed or disappears i n the change Th en t h e con
dition for e quilibrium i s :

E V O l0 g

01

V1

l0 g

01

K and the quantities

T,

oo
og

P1 g
01

depend only upon p and

and t h is d e p e nd e nc e is t o be found from the equations :
6

go o,

l og K

6p

l og K
aT

N ow ,

and

in accordance with

c
p g,

E VO

ap
( Mo
ar

6 90 1
Vl

ap

(9 90 1

ar

"
l

for any innit e ly small change of

T:
d sp o

(18 0

du o

p dvo

vodp

29 9 0

uo

d T,

THERMODYNAM I C STATES O F EQU I L I BR I UM

27

and cons e qu e ntly from

,

no

d 0 0

p oo

dT

and h e nce :
990 0

00

6p

T
"
H

ag o

vodp

6T

S imilar equat i ons h o ld for th e oth e r

log K

log K

6T

RT

Z
Z

90 s ,

2 V ovo +

V i vI

"

WW 1

V OU O

RT

and th e r e fore we g e t :

6p
6

P3 0

V i vi

or more br i e y :
,

log K

RT

ap

AV

log K

AQ

Z
RT

(7 )

6T

AV

denote the change in the total volum e of the system and

AQ the heat which is communicat e d to it from outsid e during
the i sobaric isothermal change cons i der e d We S hall now i nv e s
t ig a t e the import of these relations in a s e ries of important
applications
if

I E lec trolyti c
.

Th e

D i ss oc i a ti on

system consists of a single phase :

n oH 2 0 ,

Th e

t
r
W
a
e
f

TO

l-

n ai

transformation under consideration

V0 : V 1

: V2

= 6n 0

5n 1

consists in the dissociation of a molecule

and a molecule H 0 therefore :

6n2

11 2 0

into a molecule

V0

H ence ,

1
,

V1

co

log

1,

V2

for e qu i librium :

in accordance with
log

cl

log

02

log K

S EC OND LECTURE

28

or since
,

and

02

c1

approximately :

1,

co

log

log K

01

Th e

dependence of the concentration 0 1 upon the temperature

now follows from
AQ
6 log c 1
2

RT

6T

AQ ,

the quantity of heat which it is necessary t o supply for the

dissociation of a molec u le of H 2 0 into the io n s H and H 0 i s
in accordance wi th Arrhenius equal t o the h eat of ionization in
the neutralization of a s trong univalent base and acid i n a
dilute aqueous solution and therefore in accordance wit h the
1
recent measureme nts of W rm a nn
'

AQ

48 5 T
.

gr cal
.

Using the number

R

for the ratio of the absolute gas constant

to the mechanical equivalen t of h eat it follows t h at :
,

log

01

2 o

6T

and by integration :
10

10

log

01

log

T+

const

T his

dependence of the degree of dissociation upon the temper

ature agre e s very well with the measurem e nts of the el e ctric
conductivity of water at different temperatures by K o h lrausc h
and H e yd we ille r N oyes and Lu nd en

II
Le t

Di s s oc i a ti on

E lec trolyte

D i ss olved

t h e system consists of an aqueous solution of acetic acid :

noH2 0 ,

The

71 1 11 4

0 2 0 2,

71 311 3

62 0 2

change under consideration consists in the dissociation of a

Ad H e yd we iller, Ann

Phy

2 8 , 5 06, 1 9 0 9

T HER M ODYNA MIC S T A T E S

molec u l e

H 4 C 20
Vo

H e nce ,

into its t w o ions therefore

,

= o,

V1

V2

1,

V3

for the state of equil i br i um i n accordance wit h

,

log
or S i nce
,

E Q U ILI BR I U M

OF

02

l og

cl

log

02

log K

03

03:

02
the su m 0 1
c is t o be r e garded as known S ince the
total numb e r of the undissociated and dissociated acid mol e cul e s
is i ndep e ndent of the d e gr e e of dissociation Therefore c l and
0 2 may b e calculated from K and 0
A n experimental test of the
equation of equilibrium is possible on account of the connection
between the degr e e of dissociation and e lectrical conductivity of
the solution I n accordance wit h the el e ctrolytic dissociation
theory of Arrhenius the ratio of the mol e cular conducti v ity of
the solution i n any dilution to t h e molec u lar conductivity k
of the s olution i n innite dilution i s :

N ow

g,

C2

02

Am

since e l e ctric conduction is accounted for by the dissociat e d mole

cul e s only I t follows then with the aid of the last equation that :
,

A0

T his law of

W ith unlimited decreasing c

increases t o
dilution for binary electrolytes rst enunciated by O stwald has
been con rm e d i n numerous cases by experiment as in the case
of acetic acid
Also the depend e nce of t h e degree of dissociation upon the
temp e rature is indicat e d here in quite a n a nal ogous manner t o
that i n the e xample considered above of the dissociation of water
,

S ECOND LECTU R E

80

III Va p ori z a ti on
.

or

S oli di c a ti on

Pu re

Li qu i d

I n equilibrium the system consists of two phases one liquid

and one gaseous or solid :
,

n om o

I 771 I

no

E ach phase contains only a S ingle mol e cular comple x (the

solvent ) but the molecules i n b oth phas e s d o not ne e d to be the
same N ow if a liquid molecule evaporates or sol i dies th e n
i n our notation
,

V0

1)

I )

a nd consequently the condition for equilibr i um In accordance

with
is :
0
log K
(8 )
,

S ince

K depends only upon p and T this equation therefor e

expresses a denite relation between p and T : the law of d e
p e nd e n c e of the pressure of vapori z ation (or melting pressure )
upon the temperature or vice v e rsa Th e i mport of this l aw is
obtain e d t hrough th e consid e rati on of t h e d e p e nd e nce of th e
quantity K upon p and T I f we form t h e compl e te di ff erent i al
of the last equation there results :
,

l og K
ar

dr +

6 log K
d T,
a!
.

or i n a ccordance with
,

AQ

AV
:

I f no and vo denote t h e molecular volum e s of the two phases then :

AV

m otto

mo

0 0,

conseq u ently :
I

AQ

m ove
771 0

dl
d}

T HER M ODYNA M IC STATES

OF

E Q U ILI BR I U M

or referred t o un i t mass :
,

AQ

00

mo

00

mo

mo

dT

th e well -known formula of C arnot and C lapeyron

IV

The

Va p ori za ti o n o r S o li dic a ti on of
S u bs ta nc es

S o lu ti o n of No n-Vo la ti le

M ost aqueous salt solutions a ff ord e xampl e s Th e symbol of

the system i n this case is sinc e the s e cond phase (gas e ous or sol i d )
contains only a S ingl e mol e cular compl e x :
.

I
n o mo

n omo, n i m i , n 2 7n2 ,

Th e

chang e i s repr e sented by :

mo

'

Vo

'

m0

and hence the cond i tion of equ i librium in accordance w i th

,

log

log K

co

is :

or since to small quantities of h i gher ord e r :

,

no

n1

n2

no
n1

n2

no

lo g K

(9 )

A comparison with formula

found i n example III sho w s

that throug h the s olution of a for e ign substance there i s involved
in the total concentration a small proportionate departure from
the law of vapori z ation or s olidication which holds for th e pure
solvent O ne can expr e ss this e ith e r by saying : at a x e d pres
sure p the boiling point or the fre e zing point T of th e s olution
is di ff erent than that ( To) for the p u re s olvent or : at a x e d
pressure T t h e vapor pr e ssure or s olidication pressur e p of th e
solution is d i ffer e nt from that (p 0 ) of the pur e solv e nt Le t us
calculate the departur e in both case s
.

S ECOND LECTUR E

32

I f To be the boiling (or free z i ng te mperature ) of the pure

solvent at the pressure p th e n i n accordance w it h
1

(log K ) 1 E

0,

T0

and by subtraction of (9 ) there results :

n1

K ) T= To

l0 g K

n2

no

N ow ,

since T i s little different from

this equation with t h e ai d of

To,

w e may write i n place of

ar

no

and from this it follows that :

T

n1

To

n2

2
0

RT

AQ

720

(1 0 )

T his

i s the l aw for the raising of the b oiling p oint or for the

l owering of the freezing p oint rst d e rived by van t H off : i n the
case of freezing AQ (the heat taken from the surroundings d u ring
t h e freezing of a liquid molecul e) is n egative S ince n o and AQ
occur only a s a product i t is not possible t o infer anyt h ing from
this formula with regard t o the molecular number of t h e liquid
solvent
2
I f p 0 be the vapor pressure of the pure s olvent at the
temperature T then i n accordance with

(lo g K ) p = p

O:

and by subtraction of (9 ) there results :

(10 g K ) p = P

10 a K

n1
o

n2

no

N ow since p and p 0 are nearly equal wit h the aid of (7 ) we may

,

write :
6 10

(1)

19 0 )

AV

(
p
RT

P0 )

no

THERMODYNAM I C STATES O F EQU I L I BR I UM

33

and from this it follows i f A V be plac e d e qual t o th e volum e of

the gas e ous molecule produc e d i n th e vapori z ation of a l i qu i d
molecule :
,

m0 R T

AV

mo

mo

mo

no

This

is the law of relative d e pr e ssion of the vapor pressure

rst derived by van t H off S i nce n o and m o occur only as a
pro duct it i s not possibl e t o infer from this formula anything
wit h r e gard t o the mol e cular weight of the liquid s olvent F re
quently the factor mo /mo is l e ft out in this formula ; b ut this i s
not all owable when m o and mo are unequal (as e g i n th e
case of water )
,

V
(E

Vap o ri za ti on of

Th e

Vo la ti le
f P r p yl A l

S olu ti on of

S u c i e n tly D i lu te S olu ti o n

S u bs ta nc es

c o ho l

in

Wa te r )
.

system consisting of two phas e s is repres e nted by the

following symbol :
,

n omo, n 1 7n 1 , n 2 7n2 ,

Im I

no

Im I

n1

nz

Im

wherein as abov e the gure 0 r e fers t o the solv e nt and the

gures 1 2 3
ref e r t o the various molecular complexes of
the dissolved substanc e s B y the addition of pr i mes i n the case
of the molecular weights
mg
the possibility is
ml
left open that the various molecular complexes in the vapor
may possess a different molecular weight than i n the liquid
S ince the system here considered may experi e nce various sorts
of changes there are als o various conditions of equilibrium t o
fulll eac h of which relates t o a d e nite sort of transformation
Le t us consider rst that change whic h consists i n the vapori z a
tion of the solvent I n accordanc e with our sch e me of notation
the following conditions hold :
,

po

= 1,

mo
o

vo

m0

, ,

= 0
,

= 0,

SEC OND LECTU R E

34

and ther e fore the condition of equilibrium (6) becomes :

,

log

m0
co

log

mo

00

log K

or if one substitutes :
,

Co

n1

= 1

n2

and

no

+ mz +

ni

71 0

CO

n1

= 1

mo

n2

no

mo

l og K

72 0

I f we treat this equation upon equation (9 ) as a model there

results an equation similar t o
,

T To

R T mo
2
o

'

Il om o

H e re AQ

is the heat e ffect in the vapori z ation of on e molecul e

of the s olvent and therefore AQ /m o i s the heat eff e ct in the
vaporization of a unit mass of the s olv e nt
W e r e mark once more that the s olv e nt always occurs i n the
formul a through the mas s only and not through the molecular
number or the molecular weight while on the other hand i n t h e
case of the dissolv e d substances the molecular state i s character
i st i c o n account of th e ir i nuence upon vapori z ati on Fi nally th e
formula contains a g e neralization of the law of van t H off stat e d
above for the raising of the b oiling point i n that here i n place
of the n umber of dissolved molecules i n the liquid the difference
between the number o f dissolved molecules in unit mass of th e
liquid and i n unit mass of the vapor appears According as the
unit mass of liquid or the unit mass of vapor contains more
dissolv e d molecules th e re results for the sol ution a raising or
l ow e ring of the b oiling point ; i n the l imiting case when b oth
quantit i es are equal and the mixture therefore boils without
changing the change i n boiling point becomes equal t o zero
Of course th e re are correspond i ng l aws holding for the chang e
in the vapor pressure
,

THE R MODYNAM I C STATES O F EQU I L I BR I UM

35

us cons i der n o w a change which cons i sts i n the vaporization

of a dissolv e d molecule For this case we have i n our notation
Le t

ml

and i n accordanc e w i th

for the condition of equilibrium :

l og

m1

cl

ml

log

cl

log K

or :
cl

01

T his

equation expresses the N ernst law of distribution I f

the dissolv e d s u bstance possesses i n b oth phases the same
molecular w e ight (m 1
th e n in a stat e of equilibrium a
xed ratio of the conc e ntrations c l and 0 1 in the liqu i d and i n the
vapor e xists which d e pends only upon th e pr e ssure and t e mpera
ture B ut if the dissolved substance polymerises somewhat in
the liquid then the r e lation demand e d i n the last e quat i on a p
p e ars i n place of t h e simple ratio
.

VI

The D i s s o lved

S u bs ta nc e

on

ly

P ha s e

Pa sses

ove r

i n to the S ec o nd

cas e i s in a c e rtain sens e a S pecial cas e of th e one prec e ding

T o it belongs th at of th e s olubility of a slightly s oluble salt
rst inv e stigated by van t H o ff e g succinic acid i n wat e r The
symbol of this system is :
T his

n oH 2 0

n 1 H6 0

04

no

H6 0 4 0 4 ,

in which we d i sregard the small dissociat i on of the acid solution

T h e conc e ntrat i ons of th e individual mol e cular complexes ar e :
.

no
co

no

n1

01

no

n1

c0

1
no

For the precipitation of solid succinic ac i d we hav e :

V1

= I,
'

Vo

= 1
,

S ECOND LECTU R E

36

and therefore from the condition of equil i brium

,

l og

log K

01

hence from
,

log

6
2
RT

AQ

01

6T

means of this equation van t H o ff calculated the heat of

solution AQ from the solubility of s uccin i c acid at 0 and a t 8 5
C T he corresp onding numbers were
and
i n an arbi
t ra ry unit
Approximately then :
By

a l og

l g

1 g

01

6T

from whic h for

27 3 :

o 2 7 32

AQ

cal

that i s i n the precipitation of a molecule of succinic acid

cal are given out t o the surroundings B erthelot found h o w
ever throug h direct measurement
calories for t h e h eat
of solution
T he absorption of a gas also comes under this h ead e g
carbonic acid i n a liquid of relatively unnoticeable smaller
vapor pr e ssure e g water at not too hig h a temperature Th e
symbol of the system i s then
,

n oH2 0

Th e

n1 0 0

vaporization of a molecule
V1

Th e

no

C O2

002

corresponds to t h e values

1
,

condition of equilibrium is therefore again :

log

cl

log K

at a xed temperature and a xed pressure t h e concentration

T h e change of the coneen
0 1 of the gas in the solution is constant
i

T HER M ODYNA MIC S T A T E S

OF

E Q U ILI BR I U M

with p and T is obtained through substitution in equation

I t follows from this that :

t ra t i o n

6 10 g
6p

AV

01

RT

l og

AQ

Z
RT

01

6T

'

is the change i n volume of t he syst e m which occurs i n the

isobaric-isothermal vaporization of a mol e cul e of CO2 AQ th e
quantity of heat abs orbed in the process from outside N ow
sinc e AV repr e sents approximat e ly the volum e of a molecul e of
gas e ous carbonic acid we may put approximatel y
AV

RT

AV

and the equat i on g i ves :

l og

01

ar

29

which integrated gives :

,

log

log

01

const

0 o p,

01

i e the concentration of the dissolved gas is proportional to the

pressure of the free gas above t h e solution (law of H e nry and
B unsen ) Th e factor of proportionality C which furnishes a m e as
ure of the s olubility of the gas d e pends upon the heat effect i n
quite the same manner as i n the exampl e previously considered
A number of no less important relations are eas i ly derived as
b y-products of those found above e g the N e rnst laws con
cerning the inuence of solubility the Arrhenius theory of iso
hydric solutions etc All suc h may be obtained through the
application of the general condition of equilibrium
In
conclusion t h ere i s one oth e r case that I desire to treat h e r e
I n the historical dev e lopment of the th e ory this has play e d a
particularly important r61e
.

V II

Os m oti c

P ressu re

We consider now a dilute solution s e parat e d by a membrane

(permeable with regard t o the solvent but imp e rmeable as
regards the dissolved substance ) from the pure solvent (in the

S ECOND LECTURE

38

sam e state of aggr e gation ) and inqu i r e a s to th e condition of

equ i l i brium The symbol of the system consid e r e d we may again
take as
,

n om o, n I m I , n 2 7n2 ,

no

mo

Th e

condition of e quilibrium is also her e again expressed by

equation
val i d for a chang e of state i n which t h e t e mp e rature
and the pressure i n eac h phas e i s maintained constant Th e
only di ff erence with resp e ct t o t h e cases treated earlier is t h is
that here in the pr e s e nce of a s e parating m e mbrane between
two phases th e pressure p i n the rst phase may be different from

the pressur e p i n the secon d p h as e whereby by pressur e as

always i s to be understood the ordinary hydrostatic or mano
metric pr e ssure
Th e proof of the applicability of equation (6) i s found i n the
sam e way as this equation was deriv e d above proceeding from the
principle of incr e ase of entropy One has b ut t o remember t hat
in t h e somewhat more general case h e re considered the external
wor k i n a given change is represented by the su m p d V + p dV
w h ere V and V denote the volumes of the two individual phases
while b e fo re V denoted the t otal volume of al l phases Accord
i ngly we use inst e ad of
t o express the dependence of t h e
constant K i n (6) upon the pressure :
.

6 10 g K
6p

6 l og
'
6 19

AV

RT

AV

RT

'

1 1)

W e have here t o do with the following change :

V0

= 1

P1

= O,

Vo

= 1,

wher e by i s expressed that a molecule of the solv e nt passes out

of the solution throug h the membra n e into the pure solvent
Hence i n accordance with
,

lo g

co

lo g K ,

o r, si n c e

no

no

T H E R M ODYNA M IC S T A T E S

E Q U ILI B R I U M

OF

K d e p e nds only upon T p a nd p

I f a pur e s o l ve nt w e r e
pr e s e nt upon both s i des of the m e mbran e we should hav e
:
1 a nd p
consequ
e
ntly
co
;
p
H er e

(log K ) p = p

0:

and by subtraction of the last two equations :

l

71

= lo
g

no
nd

6 10 g K

(
1)
p
6 1,

i n accordance with
AV

(29

no

denotes t h e change i n volume of the solution due to t h e

Approximately
loss of a molecule of the s olvent
then :
H e re AV

the volume of the whole solution and

,

n1

n2

+
p

7 %

V
O

I f we call the difference p

the osmotic press ure of th e
p
solution this equation contains the well known law of osmotic
pressure due t o van t H off
Th e e q u at l o ns here derived whic h easily permit of multiplica
tion and generalization have of course for the most part not been
derived i n t h e ways described above but have been derived
either directly from experiment or theoretically from the con
sideration of special reversible isothermal cycles to whic h the
thermodynamic law was applied that i n such a cyclic process
not only the algebraic s u m of the wor k produced and th e h eat
produced but that also e ach of th e se two quantities separately is
Th e employment of a cyclic
equal to zero (rst l e cture p
process h as the advantage over the procedure here propos e d
,

S ECOND LECTU R E

40

that in it the connection between th e directly measurable quan

tities a nd the r e quirements of the laws of th e rmodynamics
succinctly appears i n each case ; b ut for each individual case a
satisfactory cyclic proc e ss must b e i magined and one h a s not
always the certain assurance th at the th e rmodynamic realization
of the cyclic process also a ctually supplies all the conditions
of equilibrium Furthermore i n the process of calculation
c e rtain terms of considerable w e ight frequently appear a s
empty ballast since they d isapp e ar at the end i n the s u m
mation over the i ndividual phases of the process
On the ot h er hand the S ignicance of the process here em
ployed consists ther e in that the necessary and sufcient condi
tions of equilibrium for each individually consider e d case appear
collectiv e ly i n the single equat i on
and that they are derived
collectiv e ly from it i n a direct manner throug h a n unambiguous
proc e dure T he more complicated the systems considered are
the more apparent becomes the advantage of this method and
there is n o doubt in my mind that in chemical circles it will b e
more and more employed especially since i n general it is now
the custom to deal directly with the energi e s and not with cyclic
processes in the calculation of heat effects in chemical cha nges
,

THI R D

L E C T UR E

O F M ATTER

T H E A TOM I C T HEORY

Th e

probl e m with which we S hall b e occupi e d i n th e pr e s e nt

lecture is that of a clos e r investigation of the at o m i c th e ory of
matter I t is however not my int e nt i on t o introduce this
theory wit h nothing further and t o s e t it up as som e thing apart
and disconn e ct e d with ot h er physical th e or i e s but I int e nd abov e
all to bring out t h e peculiar signicance of the atomic theory as
related to the present general system of theoretical physics ; for
in t h is way only will it be possible t o regard the whole system
as one containing wit h in itself the essential compact unity and
thereby t o r e alize the principal object of these lectur e s
C onsequently it i s self evident that we must r e ly on that s o rt
of treatment which we h ave recognized i n l ast week s lecture as
fundamental T hat is t h e division of all physical processes into
reversible and irreversible processes Furthermore we shall be
convinced that the accomplishment of this division i s o nl y pos
sibl e throug h the atomic theory of matter or i n other words
that irreversibility l eads of necessity t o atomistics
I h ave already r e ferred at the close of t h e rst lecture t o t h e
fact t h at in pure thermodynam i cs w h ic h knows nothing of an
atomi c structure and whic h regards all substances as absolutely
continuous the difference between reversible and irreversibl e
processes can only b e d e n e d i n one way which a priori carries
a provisional character and does not with stand p e n e trating anal
T his appears immediat e ly evident when one reects that
ys i s
the purely thermodynami c d e nition of irrev e rsibility which
proceeds from the impossibility of the realization of certain
changes i n nature as e g the transformation of h e at into
work without compensation has at the outset assum e d a d e
nite limit t o man s m e ntal capacity whil e how e ve r such a
.

41

TH I RD LECTURE

42

l i mit is not ind i cat e d i n r e ality O n th e contrary : mank i nd is

making ev e ry end e avor t o pr e ss b e yond th e pr e s e nt bo u ndari e s
of its capacity and we hope that later on many things will be
attain e d which perhaps many r e gard at pr e sent as impossible
of accomplishment C an it not happen then that a process
which up to the present has b ee n regarded as irr e versible may
be proved through a new discov e ry or i nvention t o be r e versible ?
I n this cas e the whole structure of the second law would u nd e ni
ably collaps e for the irreversibility of a S ingle process conditions
that of all the others
I t is evident then that the only means t o assure t o the second
l aw real meaning consists in this that the i dea of irr e versibility
be made ind e p e ndent of any relationship t o man and especially of
all technical r e lations
N ow the idea of irreversibility harks back t o the idea of e ntropy ;
for a process is irreversibl e when it is connected with an increase
of entropy T he problem is h e reby referred bac k t o a prop e r
improvement of t h e denition of entropy I n accordance wit h
the original denition of C lausius the entropy i s measured by
m e ans of a certain reversible process and the weakness of this
d e nition rests upon the fact that many such reversible processes
strictly speaking all are not capable of being carried out in
practice W ith some reason it may be object e d tha t we h ave
here to do not wit h an actual process and an actual physicist
but only with ideal processes s o -call e d thought experiments and
with an id e al physicist who operat e s with all the experimental
methods with absolute accuracy B ut at this point the di ff iculty
is encount e red : H o w far d o the physicist s ideal measurements
of t h is sort su ffic e ? I t may be understood by passing to the
limit that a gas is compr e ssed by a pressure which i s equal to
the pressur e of the gas and i s heated by a h e at reservoir which
possesses t h e same t e mperature as the gas but for example
that a saturated vapor shall b e transform e d through isoth e rmal
compress i on i n a r e v e rsible mann e r t o a liquid without at any
tim e a part of the vapor bein g cond e ns e d as in certain ther
.

TH E

ATOM I C THEORY O F M ATTER

43

considerations is suppos e d must c e rtainly app e ar

do u btful St i ll mor e str i k i ng ho we v e r is th e lib e rty as r e gards
thought exp e r i m e nts wh i ch in physical ch e mistry i s grant e d th e
th e orist W i th his sem i -permeabl e m e mbranes which i n real i ty
are only real i z able und e r certain sp e cial conditions and then
only with a c e rtain approx i mation he separa tes i n a r e v e rsible
manner not only all poss i ble vari e ties of molecul e s whether or
not th e y are in st able or unstable conditions but he als o sepa
rat e s the opposit e ly charg e d ions from one anoth e r and from th e
undissociat e d molecules and he i s disturb e d n eith e r by th e
enormous el e ctrostatic forc e s wh i ch res i st such a s e paration nor
by the circumstance that i n reality from the beginning of the
separation the molecules become i n part d i ssociated while the
ions in part again combine B u t such ideal process e s are nec
essary throughout in order t o make possible the comparison of
the entropy of the undissociated molecules with the entropy of
the dissociated mol e cules ; for the law of thermodynamic e qui
librium does not permit in general of derivation in any other way
in cas e one wishes t o retain pure thermodynamics as a basis I t
must be considered remarkable that all th e se ingenious thought
processes have s o well found conrmation of their results in
experience as is S hown by the examples considered by us in the
la st lecture
I f now on the other hand one r e ects that in all these results
every reference t o the possibility of actually carry i ng out each

ideal process has disapp e ared there are c e rtainly left relations
between dir e ctly m e asurable quantiti e s only such as tempera
~
ture h e at e ffect concentration e t c t h e pr e sumption forces
its e lf upon one that perhaps the introduction a s ab ove of such
ideal processes is at bottom a round -about m e thod and that
the peculiar import of the principle of incr e ase of entropy w i th
all its cons e qu e nces can be e volv e d from the original id e a of
irrev e rsib i lity or u st as w e ll fr o m th e i mposs i b i l i ty of perp e tual
motion of the second k i nd j ust as th e pr i nc i pl e of conservation
of e nergy has b e en e volved from th e law of imposs i bility of
perp e tual motion of the rst kind
m o dy n a m i c

TH I RD LECTUR E

44

step : t o have complet e d th e e mancipation of the entropy

idea from the e xperimental art of man and the el e vation of the
second law thereby t o a real principle was the scientic life s
work of Ludwig B oltzmann B riey stat e d it consisted in
general of referring back the idea of entropy t o the idea of
probability T hereby i s als o explained at the same time the
signicance of the above (p 1 7 ) auxiliary term used by me ;
pr e ference of nature for a denite state N ature prefers the
more probable states t o the less probable because i n nature
process e s take p la Ce in the direction of greater probability H eat
goes from a b ody at higher t e mperature t o a b ody at low e r
temperature because the state of equal temperature distribution
is more probable than a state of unequal temperature distribution
T hroug h this conception the second law of thermodynamics
is removed at one stroke from its is olated position the mystery
concerning the preference of nature vanishes and the entropy
principle reduces t o a well understood law of the calculus of
probability

Th e enormous fruitfulness of s o obj ective

a denition of
entropy for all domains of physics I shall seek t o demonstrate
in the following lectures B ut today we have principally t o do
with the proof of its admissibility ; for on closer consideration we
shall immediately perceive that the new conception of entropy
at once introduces a great number of questions new requirements
and difficult problems T he rst requirement is the introduction
of the atomic hypothesis into t h e system of physics For if one
wis h es t o speak of the probability of a p h ysical state i e if he
wishes t o introduce the probability for a given state as a denite
quantity int o the calculation this can only be brought about as
in cases of all probability calculations by referring t h e state back
to a variety of possibilities ; i e by considering a nite number
of a priori equally likely congurations (complexi ons ) throug h
each of w h ich the state considered may be realized The greater
the number of complexions the greater i s the probab i lity of the
state T hus e g the probability of throwing a total of four
This

ATOM I C THE O RY OF MATTE R

TH E

45

with two ord i nary six-sid e d dic e is f o und through counting th e

compl e x i ons by which the throw w i th a total of four may be
reali z ed Of these th e r e ar e thr ee compl e xions :
.

with the rst d i e

with the rst di e
with th e rst d i e

1,

2,

3,

with the s e cond die

w i th the second die
w i th th e second die

3,

2,

O n the other hand th e throw of two i s only r e alized through

a single complexion T h e r e fore the probab i l i ty of throwing a
total of four is three times as great as th e probab i lity of throwing
,

a total of two
N ow i n connection with the physical state under consideration
i n order to b e able t o differ e ntiate compl e t e ly from on e another
the complexions real i z ing it and to associate it with a denit e
reckonable number there is obviously n o oth e r means than to
regard it as made up of numerous discrete homogeneous elements
for in p e rf e ctly continuous systems there exist n o reckonable

e lements and h e r e by the atomistic vi e w i s made a fundamental

requir e m e nt W e hav e th e r e for e t o r e gard all bodi e s i n nature
in so far a s th e y poss e ss a n e ntropy as constituted of atoms and
we th e refore arrive in physics at the same conc e pt i on of matter as
that which obtained i n ch e mistry for s o l ong pr e viously
B ut we can immediat e ly go a step furth e r y e t Th e conclu
sions r e ach e d h e ld not only for thermodynamics of material
bod i es but als o possess compl e t e validity for th e process e s of
h e at radiation whic h are thus referred back t o the second law
of thermodynamics T hat radiant heat also possesses an e ntropy
follows from the fact that a b ody which emits rad i ation into a sur
rounding diathermanous medium experienc e s a l oss of h e at and
therefor e a decrease of e ntropy S ince the total entropy of
a physical system can only increase it follows that one part
of the entropy of the whole system consisting of the body and the
diathermanous med i um must b e contained in t h e radiated h e at
I f the entropy of t h e radiant h e at is to be r e f e rred back t o the
notion of probabil i ty w e are forced in a sim i lar way a s abov e t o
.

TH I RD LECTURE

46

the conclusion that for radiant heat the atomic conc e ption
possesses a den i te m e an i ng B u t S i nce radiant heat is not
dir e ctly connected with matter it follows that th i s atomistic con
c e p t i o n r e lates
not t o matter but only t o energy and hence
that in heat radiation certai n energy elements play an essential
r61e
E v en thoug h this conclusion appears s o singular and even
though in many c i rcles t oday vigorous obj ection i s strongly urged
against it i n the l ong run physical researc h will not be able
to withhold its sanction from it and the less since it is conrmed
by experience i n quite a satisfactory manner We shall return
to this point i n the lectures on heat radiation I desire here
only t o mention that the nov e lty involved by the introduction
of atomistic conc eptions int o the the ory of heat radiation is by no
means s o revolutionary a s p e rhaps might appear at the rst
glance For there i s in my opinion at least nothing whic h makes
necessary the consideration of the heat processes i n a complete
vacuum as at omic and it su ffices t o s eek the atomistic features at
the s ource of radiation i e i n thos e proc e sses which have
their play i n the centres of emission and abs orption of radiation
T hen the M axwellia n electrodynamic differential equations can
retain completely their validity for the vacuum and besides
t h e discrete elements of heat radiation are relegated exclusively
t o a domain which is still very myst e r i ous and where there is
still pres e nt plenty of room for all s orts of hypotheses
R eturning to more general consid e rations the most i mportant
question com e s up as t o whether with the introduction of a t o m i s
tic conceptions and with the reference of entropy t o probability
the content of the principle of increase of entropy is exhaustively
compreh e nded or whether still further physical hypotheses are re
quired i n order t o secure t h e full i mport of that principle I f this
important qu e stion had be e n s e ttl e d at the time of the i ntro
duction of t h e atomic th e ory int o th e rmodynamics then the
atomistic views would surely have been spar e d a large number of
conc e ivabl e misunderstandings and j ustiabl e attacks For it

turns out in fact and our further considerations will con

.

ATOM I C T H E ORY O F M ATTER

TH E

47

rm this conclusion that th e re has as y e t noth i ng be e n don e with

atom i stics which i n its e lf r e quir e s much more than a n essen
tial g e n e rali z ation in order to guarantee the validity of the
second law
W e must rst r e ect that i n accordance with the central
id e a la i d d own i n th e rst l e cture (p
the second law must
poss e ss val i d i ty as a n objective physical law i nd e p e nd e ntly of
the individual i ty of the physicist T h e r e i s nothing t o hinder

us from i magining a physicist we shall designate him a mi

c ro sc o p i c
observer whose s e nses are s o sharp e n e d that he
is able t o recogni z e eac h individual atom and to follow it in
its motion For this obs e rver each atom moves exactly i n
accordance with the elementary laws which g e n e ral dynamics
lays down for it and th e se laws allow s o far as we know of an
inverse p e rformance of every process Accordingly here again
the question is neither one of probability nor of e ntropy and its
increase Le t us imagine on the other hand another o b

server designated a macroscopic observer who regards an

ensemble of atoms as a homogeneous g as sa y and consequently
applies the l aws of th e rmodynamics t o the mechanical and th e rmal
processes within it T hen for such an obs e rv e r i n accordance
wit h the second law the process i n general is a n irreversibl e
process W ould not now the rst observ e r be j usti e d i n saying :
The r e ference of the entropy t o probability h a s its origin in
the fact that irreversibl e proc e ss e s ought to be expla i n e d t h rough
reversible process e s At any rate this procedure appears to me
in the highest degree dubious I n any case I d e clar e e ach change
of state whic h takes place in the ens e mble of atoms d e signat e d
a gas a s reversible i n opposition t o the macroscop i c obs e r v er
T h e re is not t h e slightest t h ing so far as I kno w that one can
urge against t h e validity of these stat e m e nts Bu t d o we not
thereby pl ace ourselves in the painf u l position of the j udg e who
declared i n a trial th e correctn e ss of the p osition of each separat e ly
of two contending parti e s and then when a third cont e nds that
only one of the parties could em e rg e from th e proc e ss victorious

TH IR D LECTUR E

48

was obliged t o declare him als o correct ? Fort unately we nd our

selves i n a more favorabl e p osition We can certainly m e diate
betw e en the two parties without its being necessary for one or
the other t o give up h is principal p oint of vi ew For cl os e r
consid e ration shows t h at the w h ole controversy rests upo n a mis

understanding a new proof of h ow necessary it is before one

begins a controversy t o come t o an understanding wit h h is
oppon e nt concerning the subj ect of the quarrel C ertainly a
given change of state cannot be b oth reversible and irreversible
B ut the one obse rver connects a wholly di ff erent i dea wit h t he

p h rase change of state than the other Wh at i s t h en in

general a c h ange of state ? Th e state of a physical system cannot
well b e otherwise dened than as the aggregate of all those p h ys
ical quantities t h rough whose instantaneous values the time
changes of the quantities wit h given b oundary c onditions are
uniquely determined I f we inquire now i n accordance with
the import of this denition of t h e two observers a s t o what
they understand by the state of t h e collection of at oms or the
gas consider e d they will give quite diff e rent a nswers The
microscopic observer will mention those quantities whic h deter
mine t h e position and the vel ocities of all the i ndividual at oms
T here are present i n the simpl e st case namely that i n which
the atoms may b e considered as material points six times as many
quantiti e s as atoms namely for each atom the three coordinates
and the three velocity components and i n the case of combined
mol e cules still more quantities For him the state a nd th e
progress of a process is then rst det e rmined when all these
various quantities are individually giv e n W e shall designate

Th e macro
the state dened in this way the micro -state
scopic observer on the other hand requires fewer data H e will
s a y that the state of the homogeneous gas considered by him is
d e t e rmined by the density the visibl e velocity and the tempera
ture at each point of the gas and he will expect that when these
quantities ar e g iv e n t he ir time variations and therefore the prog
ress of the proc e ss to be completely det e rmin e d i n accordanc e
.

THE

ATOM I C THEO R Y O F MATTER

49

with the two laws of thermo -dynamics and ther e fore accompani e d
by a n incr e ase i n entropy I n this connect i on he can call upon
all the experience at his disposal whic h will f u lly conrm his ex
-state
i
I
f
we
call
this
state
the
macro
it i s cl e ar that
e
c
t
a
t
o
n
p

the two laws : the micro-changes of state are reversible and

t h e macro-changes of state are irrev e rsible lie i n wholly
di fferent domains and at any rate are not contradictory
B ut now how can we succeed i n bringing the two observers t o
a n understanding ? This is a question whose answer i s obviously
of fundam e ntal signicance for the atomic th e ory First of all
it is easy to s e e that the macro-observer reckons only wit h mean
values ; for what he calls density visible velocity and temperature
of the gas are for the micro-observer certain mean values statis
tical data which are derived from the space distribution and from
t h e velocities of the atoms in an appropriate manner B ut the
micro-observer cannot operate with these mean valu e s alone for
if these are given at one instant of time the progress of the process
is not det e rmined throughout ; o n the contrary : he can easily
nd wit h given mean values an enormously larg e number of
individual values for the positions and the vel ociti e s of the atoms
all of which correspond with the same mean values and which i n
spite of this l ead t o q u ite di fferent proc e ss e s with r e gard to the
mean values I t follows from this of n e c e ssity that the micro
observer must either giv e up the attempt to u nd e rt a nd the unique
progress in accordance wit h experience of t h e macroscopic
changes of state and t h is woul d b e the end of the atomic theory
o r that he t h roug h the introduction of a special physical
hypothesis restrict i n a suitabl e manner the manifold of micro
states considered by him T here is certainly nothing to prevent
him from assuming that not all conc e ivable micro -states are
realizabl e in nature and that certain of them are in fact thinkable
but never actually r e ali z ed I n the formulari z ation of such a
hypothesis there is of course n o point of d e parture t o be found
from the principles of dynamics alon e ; for pure dynamics leaves
this case undetermin e d B u t on ust this account any dynam i cal
,

TH IR D LECTUR E

50

hypothesis whic h involves nothing furth e r than a cl oser S p e c i

cation o f the micro -stat e s real i ze d i n natur e i s certainly p e rmis
sible Which hypothesis is t o be given the preference can only
be decided throug h comparison of t h e results t o which the
different possible h ypotheses lead i n the course of experience
I n order t o limit th e investigation i n this way we must obviously
x our attention only upon all i maginable congurations and
velocities of the individual atoms which are compatibl e with
determinate valu e s of the density the velocity and the temper
ature of the gas or i n other words : we must consider all the
micro -states which b e long t o a determinate macro-state and
must investigate the various kinds of proc e sses whic h follow i n
accordance with the xed laws of dynamics from the different
micro-states N ow precise calculation has in every case always
led t o the important result that an enormously large number of
these different micro-processes relate t o one and the same macro
process and that only proportionately few of the same which are
distinguished by quite special exceptional conditions concer ning
the positions and the vel ocities of neighboring atoms furnish
exceptions Furthermore it has also shown that one of the
resulting macro -processes i s that which t he macroscopic o b
server recogni z es s o that it is compatible with the second law
of thermodynamics
Th e
H ere manifest ly the bridge of understanding is supplied
microobserver n e eds only t o assimilate in his theory the physical
hypothesis that all those S pecial cases in which special exceptional
conditions exist among the neighboring congurations of inter
acting atoms do not occur i n nature or i n other words that the
micro -states are i n elementary disorder T hen t h e uniqueness
of the macroscopic process i s assured and with it also the f u lll
ment of the principle of increase of entropy i n all directions
T herefore it is not the atomic distribution but rather the
hypothesis of elementary disorder whic h forms the r e al kernel of
the principl e of increase of entropy and ther e for e the pre
liminary condition for th e exist e nce of e ntropy Without ele
,

ATOM I C THE O RY O F MATTE R

TH E

51

ment a ry disorder there is n e ith e r ent ropy nor irreversibl e proc e ss

T herefore a single atom can nev e r possess an entropy ; for we
cannot speak of d i sorder i n connect i o n with it B u t wit h a
fairly large number of atoms s a y 1 0 0 or
the matter is
quite di ff erent H er e one can c e rta i nly sp e ak of a disord e r i n
case that the values of the coordinates a nd the velocity com
p o ne nt s a re distribut e d among the atoms i n accordance wit h the
laws of acc i dent T h e n it i s possible t o calculate the probability
for a giv e n state B ut how i s it wit h regard t o the increase of
entropy ? M a y we assert that th e motion of 1 0 0 atoms is irre
v e rsib le ?
C ertainly not ; b ut this is only because the state of
1 0 0 atoms cannot be dened i n a thermodynamic s e ns e since the
process do e s not proceed i n a unique manner from th e standpoint
of a macro -observer and this r e quirem e nt forms as we have s ee n
above the foundation and preliminary condition for the denition
of a thermodynamic state
I f o ne therefore asks : H o w many atoms are at l e ast necessary
in order that a proc e ss may be considered irr e v e rsibl e ? the answer
is : s o many atoms that one may form from th e m denite mean
values which d e ne the state i n a macroscopic sense O ne must
reect that t o se c u re the v alidity of the principl e of incr e ase of
entropy there must be add e d t o the condition of elementary d is
order still a nother namely that t h e numb e r o f the el e ments
under considerati o n be su fciently larg e t o r e nder possible the
formation of denite mean valu e s Th e second law has a
m e aning for these mean values only ; but for them it is quite
l

h e p h y i i t wh in p it e f ll thi reg rd the hyp the i f

el em e t r y di rder gr t it
i rre t I wi h t r efer th e imp le
i i t f f ri ti
l l ti f
f diff i
f he t
f t th t i ever y
d ti f r m m le l r
ider ti the n ti f el em e t ry di rder
therwi e d th t i t i th ref re e e ti ll y
i em p l yed wh eth er t itl y
diti i te d f i g ri g
e li g i t B t
m r e rr e t t ti p l t e thi
h e wh reg rd th e h yp the i f elem e t r y di rder
l f evide t h ld
rd e with l w f H P i e the p re i e i
b r em in d ed th t i
er i g th e f d ti
f whi h w ld h er e l e d
t
f
tig t i n
ll ti m e i
the
m p ti
f thi h y p th e i f
w rr ted f
l ed

l
l
e
w
ith
b
l
t
e
l
y
m
th
w
i m p rt t
l i
t whi h
g i
p
l y b rged the f t th t b l tel y m th w ll d t e i t i t re
To t

n a

c on

v es

on o

c an on

e u

so u

or o

ac

an

or a

S,

so u

oo

o r c o nc

a s se

o nc ar

ou

c s

an

o no

us

oo

a r,

or a c os

c o nc us o n , a

an

ss n

s un

so

ou

an

n a

so

u s on, o r O

on o

no

o n, o

on o

n a

s s

oo

oun

s s o

s,

o ns ,

o n ns

anc

n n

c en

s s o

n ac c o

nco

s c on

u a

a c oe

c o ns

c onc

a ss u

ac

on o

cu a

ous or a s

a u

ac

o s

co

o,

ca cu a

on,

uc

as

so

ac

s c s s

os

x s

a ns

n na u

TH I RD LECTU RE

52

exact j ust as exact as the law of t h e calculus of probability that

the mean value s o far as it may be dened of a su fciently large
number of throws wit h a S ix -sid e d die i s
T hese considerations are at the same time capable of t h rowing
ligh t upon questions suc h a s t h e foll owing : D oes t h e principle of
increase of entropy possess a meaning for the s o -called B rownian
molecular movement of a s uspended particle ? D oes th e k inetic
energy of this motion represent useful work or not ? T he entropy
principle i s j ust a s little valid for a single suspended part icl e as
for a n at om a nd t h erefore is not valid for a few of them but
only when there is s o large a number that denite mean values
can b e formed T hat one i s a ble t o s e e the particles a nd not
the atoms makes n o material di fference ; because the progress of a
process does not depend upon the power of a n o b se rv m g Inst ru
ment T he question wit h regard t o useful work plays n o r61e
in t h is connection ; strictly speaking t h is possesses in general n o
For it d oes not admit of an answer
o bjective physical meaning
without r e ference t o t h e sch eme of th e physicist or technician
who proposes t o make u se of the wor k i n question Th e second
law therefore has fundamentally nothing t o d o wit h the id e a of
useful work (cf rst lecture p
B ut if the entropy principle is to h old a furt h er assumption is
necessary concerning the various disordered elements a n
assumption whic h tacitly is commonly made a nd which we
have not previously d enitely expressed I t is however n o t
less important than those referred t o ab ove T he elements must
actually b e of the same k ind or they must at least form a number
of groups of like k ind e g constitut e a mixture in whic h each
kind of element occurs i n large numbers For only t h roug h the
similarity of t h e elements d oes it come about t h at order and law
can result i n t h e larger from the smaller If the molecules of a
gas b e all different from o n e another the properties of a g as can
never S how s o simple a l aw -abiding behavior a s that which is
indicat e d by th e rmodynamics I n fact the calculation of t he
probability of a state presuppos e s that all complexions which
,

TII E A T O MIC THE O RY

OF

M ATTER

correspond t o the state ar e a priori equally l i k e ly W ithout

this condition one i s ust a s little able t o calculat e th e probability
of a giv e n state as for instanc e the pr o bability of a given throw
wit h dice whose sid e s are unequal i n si z e I n summing up we
may therefore sa y : the s e cond law of thermodynamics i n its
objective physical conception fr ee d from anthropomorphism
r e lat e s t o certain mean valu e s which are form e d from a large
number of disordered elem e nts of the same kind
T he validity of the principl e of i ncrease of e ntropy and of t h e
irreversible progress of thermodynamic process e s i n nature is
completely assured i n this formulari z ation After the intro
duction of the hypothesis of elementary disorder the microscopic
observer can n o l onger con dently assert that each process con
s i de re d by him in a collection of atoms is reversible ; for the
motion occurring i n the reverse ord e r will not always obey the
requirements of that h ypothesis I n fact the motions of single
atoms are always reversible and t h us far one may s a y a s before
that t h e irreversible processes appear reduc e d t o a reversible
process b ut t h e p h enomenon a s a whole is nevertheless i rre
because upon reversal the disorder of t h e numerous
v e rsible
individual elementary processes woul d be eliminated Irre
v e rsi bili t y i s inherent not i n the individual elem e ntary processes
themselves b ut s olely i n their irregular constitution It is
this only wh i c h guarantees the unique change of the macroscopic
mean values
T hus for e x ample t h e reverse progress of a frictional process
i s impossible i n that it woul d presuppose elementary arrange
ment of interacting neighboring molecules For the collisions b e
tween any t wo molecules must thereby possess a certain distin
i
hi
n
c
h
aracter
i
n
that
the
velocities
of
two
colliding
molecules
s
u
g
g
depend in a denite way upon the place at which t h ey meet
I n this way only can it h appen that i n collisions li ke directed
velocities ensue and th e refore visible moti on
Previously we have only r e ferred t o the principle of elementary
disorder in its application t o th e atomic the ory of matter B u t
.

'

TH I RD LECTURE

54

it may als o be assumed a s valid as I wis h t o indicate at this

point o n quite the same grounds as those hold i ng i n the case of
matter for the theory of radiant h eat Le t us consider e g
t w o bodies at diff e r e nt temperatures b etwe e n whic h exchange of
heat occurs throug h radiation W e can i n this case also imagine
a microscopic observer a s opposed t o the ordinary macro
scopi c observer who p ossesse s insight int o a ll the particulars
of electromagnetic processes whic h are connected wit h emission
and a bsorption a nd the propagation of heat rays T he micro
scopi c o bserver w
ould declare the whole process reversible
because a ll el e ctrodynamic processes can also take place i n the
reverse direction and the contradiction may h ere b e r e ferred
bac k t o a difference i n denition of the state of a h eat ray T hus
w h ile the macroscopic O bserver c ompletely denes a mono
ch romatic ray t h roug h direction state of polarization color and
intensity the microscopic observer i n order t o possess a complete
k nowledge of a n electromagneti c state necessarily requires the
specication of all the numerous irregular variations of amplitude
and p h ase t o whic h the most h omogeneous h eat ray i s actually
subj ect Th at s uc h irregula r variation s actu ally e x ist follows
immediately from t h e well k nown fact that two rays of the same
color never interfere e x cept when they originate in t h e same s ource
of lig h t B ut until these uctuations are given i n all p articulars
t h e micro -observer can s a y nothing wit h regard t o the progress
of t h e process H e is als o unable t o specify w h ether the e x change
of h eat radiation b e twee n the two b odies leads t o a decrease or
to a n increase of their di ff erence in temperature T he principle
of e lementary disorder rst furnishe s the adequate criterion of
t h e tendency of the radiation process i e the warming of the
colder b o dy at the expense o f the warmer ust as the same princi
ple conditions the irreversibility of exchange of heat throug h con
duction H owever in the two cases compared there is indicated
an essential diff e r e nce in the k ind of the disorder While in
h e at conduction the disordered el e ments may be represented
as associat e d with th e various molecules in heat radiation there
,

TH E

ATOM I C THEORY

or

MATTER

55

ar e th e numerous v i brat i on p e r i od s c o nn e ct e d w i th a neat ray

among wh i ch the e n e rgy of rad i at i on i s i rr e g u l a rly d i str i but e d
I n oth e r words : the d i sorder among th e m o l e c u l e s is a mat e rial
on e W hil e in h e at rad i ation it is on e of e n e rgy d i str i but i on T h i s
is the most important diff e renc e b e t w e e n the t w o kinds o f d i s
order ; a common f e ature exists as regards th e great number of
uncoordinat e d e l e m e nts r e qu i red J ust as the entropy of a b o dy
is dened as a funct i on of the macroscopic stat e only w hen the
body contains s o m any atoms that from them d e nite mean
valu e s may be formed so the e ntropy principle only poss e ss e s
a meaning with regard t o a heat ray when th e ray compr e hends
persists for so long a tim e that
s o many periodic vibrations i e
a denite mean value for the intensity of the ray may be obtained
from the successive irregular uctuating amplitudes
N ow after the principle of elementary disorder has been
introduced and acc e pted by us as valid throughout nature the
fundamental question aris e s as to the calculation of the proba
b ilit y of a given state and the actual derivation of the e ntropy
therefrom From the entropy all the la w s of thermodynamic
states of equilibrium for material substanc e s and also for
may be uniquely derived W it h regard t o
e nergy radiation
the connection between entropy and probability this is inferr e d
very simply from the law t h at th e probability of two independent
congurations is represented by the product of the individual
probabilities :
IV
W1 W2
,

while the entropy S is repr e sent e d by the

entropies :
S
Accordingly the
,

e ntropy

is

SI

S2

su

of the individual

proportional t o the logarithm of the

probability :
S

to log lV

(1 2)

a universal constant I n particular it is the same for atomic

as for radiation congu rations for th e re i s nothing t o pr e vent

k is

TH IR D LECTU R E

56

us assuming that the conguration designated by 1 is atomic

while that designated by 2 is a radiation conguration I f It has
been calculat e d sa y with the aid of radiation measurements
then It must have the same value for atomic processes Later
we shall follow this proc e dure in order t o utilize the laws of heat
radiation in the kinetic theory of gases N ow t h ere remains as
the last and most di f cult part of the problem t h e calculation of
the probability W of a given physical c onguration i n a given
macroscopic state We shall treat t oday by way of preparation
for t h e quite gen eral problem t o follow the simple problem : t o
specify the probability of a given state for a single moving
material point subj ect to given conservative forces S ince t h e
state depends upon 6 variables : the 3 generalized coordinates
pl
p 2 p 3 and t h e t h ree corresponding velocity components
and since all possible values of these 6 variables con
31 62
the probability sought is t h at
st i t u t e a continuous manifold
these 6 quantities shall lie respectively within certain innitely
small interval s or if one t h inks of these 6 quantities as t h e
rectilinear ort h ogonal coordinates of a point i n an ideal S i x-di

m e nsi o nal space t h at this ideal state point shall fall within

a given innitely small state domain

S ince t h e domain is
innitely small the probability will be proport ional t o the mag
nit u d e of t h e domain and therefore proportional to
,

d<
P2

OI

d Pl

d sbz

d ies

B ut t h is expression cannot serve as an absolute measure of

the probability because i n general it changes in mag nitude wit h
the time if eac h state point moves in accordance wit h the laws
of motion of material points while the probability of a state
whic h follows of necessity from anot h er must be the same for
the one as the other N ow as i s well k nown another integral
quite similarly formed may b e specied i n place of t h e one
a bove w h ic h possesses the special property of not changing in
value wit h t h e time I t is only necessary t o employ i n addition
to the general coordinates p 1 p 2 gas t h e t h ree s o-called momenta
,

TH E

ATOM I C THEORY OF MATTER

57

in plac e of the thr ee v e loc i ti e s c 1 62

as th e d e ter
mining coordinates of the state Th e se are d e n e d in the
following way :
l

i l,

$1

by

$0 3

denot e s the kinetic potent i al (Helmhol z )

H am i ltonian form the equations of motion ar e :
wherein H

T hen

in

d 0 1
1

90 1

dt

3E

apl

(E is the e ne rg and from these equations follows the c o n

,

dition of incompressibility
6 95 1

(a

at .

to the six -dimensional space represent e d by the c o o rd i

nates 2 1 p g 90 3
this e quation states that the magnitude
$2
of an arbitrarily chosen state domain viz :

R eferring
,

d0 1

d se s

d so z

dlpi

dips

d o e s not change with the time when each p oint of the domain
changes it s position in accordance wit h t h e laws of motion of
material points Accordingly it is made possible t o take the
magnitude of this domain as a direct measure for the prob
ability that the state point falls within the domain
From the last expression whic h can be easily generali ze d for
t h e case of an arbitrary number of variables we S hall cal
u la t e later the probability of a thermodynamic state for the
case of radiant energy as well as that for material substanc e s
,

F O UR TH

TH E E Q UAT I O N

OF

L E C T UR E

S TATE

M O N ATOM I C GAS

FOR

M y problem t oday is t o utilize the general fundamental laws

concerning the concept of irr e vers i bility which we established
in the lecture of yest e rday i n the s olution of a d e nite problem :
the cal culation of the entropy of an id e al monatomic gas i n a
given state and the derivation of all its thermodynamic proper
ties T he way i n which we have t o proceed is prescribed for u s
by the general denition of entropy :
,

l og W

(1 3)

chief part of our problem is t h e calculation of W for a given

state of the gas and i n this connection there I s rst required a
more precise investigation of that which is t o be understood as
the state of the g a s O bvi ously the stat e i s t o be taken here
sol e ly in th e s e nse of the conception which we have called macro
scopic i n the last lecture Otherwise a state would poss e ss
neither probability nor entropy Furthermore we are not
allowed t o assume a condition of equilibrium for the gas For
this is charact e ri ze d throug h the further Special condition
that the entropy for it i s a maximum Th us an unequal d i s
t ri b u t i o n of density may exist i n the gas ; also there may b e
present an arbitrary number of d i ffer e nt currents and i n general
no kind of e q uality between the various velocities of the molecules
is to be as s umed Th e velocities as the coordinates of the
m o l e cul e s are rather t o b e taken a priori a s quite arbitrarily
given but i n order t h at the state consider e d in a macroscopic
sense may be assumed as known ce rtain mean values of the
densiti e s and the vel ociti e s must exist Throug h these mea n
Th e

58

E QUAT I O N O F STATE

M O NATOM I C G AS

FOR

59

valu e s the state from a macrosc o pic standpo i nt is compl e tely

characterized
Th e cond i tions m e nt i on e d wil l a ll be fulll e d if w e consider
the state as giv e n i n such mann e r that the numb e r o f mol e cul e s
in a sufciently small macroscop i c sp a c e but which ho weve r
contains a v e ry large number of mol e cul e s is g i v e n and furth e r
more that the (likewise great ) numb e r o f th e s e mol e cul e s is
given which are found i n a certain macroscopically smal l v e l oc i ty
domain i e whose velociti e s lie within certain small int e r v als
I f we call the coordinates a i z and t h e v e locity compon e nts
1
73 y
then this number will be proportional to
.

dx -dy -dz -dx -dy

I t will depend besides upon a nite factor of proporti onality

"
which may be an arbitrar i ly giv e n function f (a y z a} y z ) of
the coordinates and the velociti e s and which has o nly th e one
condition t o fulll that
,

2f

N,

(1 4 )

where N denot e s the total number of molecules in the gas

We are now concerned with the calculation of th e probab i l i ty
W of that state of the gas which corr e sponds t o th e arbitrarily
giv e n distribution function
T he probability that a given mol e cule p ossesses suc h coor
d ina t e s and suc h velocities that it l ies within the domain a is
expressed i n accordance with t h e nal r e sult of the pr e vious l e c
ture by the magnitude of the corresponding elementary domain :
.

d90 2

d sDI

ds0 3

dsbz

s,

th e refore s i nce here

,

W m

m r -diff ere ti l i
ll
tr di ti ti t the mi r d if
W
i it l y m ll with refere e t th e di m e i
f a
t i l whi h
f
b etwee p h y i l
I p r efer thi t er m i l g y f O th e di ri m i ti
m le le
e f p hr i g b e
e
d m th em ti l di ff ere ti l i
p it e f th e i el eg
th e m r -di ff ere ti l i l j t m h m them ti l p hy i l d the
m h p hy i l
m them ti l
m i r di ffere ti l j t
$0
1

an

a re

ca

ac o

c o-

us

as

n c on

a s

n s

a so

us

as

ml

nc

uc

no o

ac o

a a

mx)

$1

z,

$0 3

'

a s

cu

y)

$0 2

e c an c a

e re n
o

x:

s ca

uc

as

on

ca

ca

n s o ns

an c

on

na

sc

nc

as

as n

s ca

s ca

c aus

an

F OURTH LECTUR E

60

(m the mass of a mol e cule) by

m

dimensional state d omain

we divid e the whol e of the six

containing all the molecul e s into suitabl e equal elementary
3
d omains of the magnitude m a Then the probability that a
given molecule fall in a given elementary domain is equally
great for all suc h doma i ns Le t P denote the number of these
equal elementary domains N ext l e t us imagine a s many dice
as there are molec ul e s pres e nt i e N and each die t o b e
provided with P equal sides Upon these P sides we imagin e
t o P s o that eac h of the P sides indicates
numbers 1 2 3
a given elementary domain T hen each thr ow wit h t h e N
dice corresponds to a given state of the gas w h ile the number of
dice whic h S how a giv e n number corresponds t o the molecules
whic h lie in the elementary d omain considered I n accordance
with this each single die can indicate with the same probability
eac h of the numbers from 1 t o P corresponding t o the circum
stance t h at eac h molecule may fall wit h equal probability in any
one of the P elementary d omains T he probability W sought
of the given state of the molecules corresponds therefore to
the number of different k inds of throws (complexions) through
which is r e alized the given distribution
Le t us take e g
N equal t o 1 0 molecules (dice ) and P
6 elementary domains
(sides ) and let us imagine the state s o given t h at there are
N ow

molecul e s
molecules
molecules
molecul e
molecules
molecules

3
4

0
1
0
2

in l et
in 2 d
in 3d
in 4 t h
in 5 t h
in 6t h

elementary domain
elementary dom ain
elementary domain
elementary domain
elementary domain
elementary domain

then this state 6 g may be r e alized throug h a t h row for which

the 1 0 d i c e indicate the following numbers :
,

l st

2d

3d

4th

5th

6t h

7 th

8 th

9t h

l 0t h

EQUAT I O N O F STATE

F OR

MONATOM I C G AS

61

Und e r

each O f the charact e rs repr e s e nting th e t e n dic e stands

the number which t h e d i e indicates i n the throw I n fact
,

3
4
0
1

0
2

dice S how
dice S how
dice S how
die S ho w s
d i ce S how
dice show

the
the
the
the
the
th e

gure
gure
gure
gure
gur e
gure

1
2

3
4
5
6

Th e

state i n question may like w ise be reali z ed throug h many other

complexions of this kind The numb e r s ought of all possible
complexions is now found throug h consideration of the numb e r
series indicated i n
For since the number of molecules
(dice ) is given the number series contains a xed number of
elements (1 0
N)
Furthermore since the number of molecul e s
falling i n an elementary d omain is given eac h number i n all
permissible complexions appears equally often i n the series
Finally eac h change of t h e number conguration conditions a
new complexion T he number of possible complexions or the
probability W of t h e given state is therefore equal t o the number
of possible permutations with rep e tition und e r the conditions
mention e d I n the simpl e e xampl e chosen i n accordance wit h
a well known formula the probability i s
.

10 l

T herefore ,

in the general case :

N!

II (f

T h e S ign II

denotes the product ext e nded ov e r all of the P

e l e mentary d omains
From this there results i n accordance with equation
for
the entropy of the gas i n the giv e n state :
.

k l o g N i kE
'

l og (f

F OUR TH LECTUR E

62

Th e

summation i s t o be extended ov e r all d omains 0

S ince
o
f a is a large quantity Stirling s formul a may b e employed for
its factorial w h ich for a large number n i s express e d by
.

(1 6)

therefore neglecting unimportant terms :

,

l og

(log

and hence :
S

[c

l og

N!

f a ao g

or if we n ot e that a and N
of state :
S
const

r e main constant i n al l changes

Ef a

(1 7 )

log f

k) the same as that

quantity is to the univ e rsal factor
whic h L B oltzmann d e no t e d b y H and whic h h e showed to
vary i n one direction only for all change s of state
I n particular we w i ll n ow d e t e rmin e the entropy of a gas i n a
state of equ i librium an d inquire rst as t o that form of the l aw of
distribution whic h corresponds t o t h ermodynamic equil i brium
I n accordance with the second law of thermodynamics a state
of equilibrium i s characteri z ed by t h e condition that with given
values of th e t otal volume V and the t otal e n e rgy E the entropy
S assumes its maximum valu e I f we assume the t otal volume
of the gas

T his

and the total energy

E

a re

22

(1 8 )

as given then t h e condition :

,

68

must hold for the state of equilibrium or i n accordance with

,

2 (10 g f

+ 1)

'

5f

'

0,

(1 9 )

EQUAT I ON O F STATE

F OR

M ONATOM I C G A S

63

wh e r e in th e var i at i on 5f r e fe rs to an arb i trary change i n the

law of d i str i but i on compatibl e with the given values of N V
and E
N ow w e hav e on account of the constancy of the total number
of molecules N in accordanc e with
,

2 6f

and on account of th e constancy of th e total en e rgy in accord

ance with
2
2
2 (e + y +
5f
a
0
,

C ons e quently for the f u lllment of cond i t i on (1 9 ) for all p e r

missible values of (if it is su f cient and n e cessary that
,

lo g f

const

or :

f
wherein oz and B are constants I n the state of equilibrium
therefore the space distribution of mol e cules i s uniform i e
independent of x y z and the distribution of velocities is the
well known M axwell i an distribution
Th e values of the constants or and B ar e to be found from those
of N V and E For the substitution of the value found for f
in (1 4 ) leads to :
.

and the substituti on of f i n (1 8 ) l e ads to :

E

E Vm 9

From t h ese equations it follows that :

3m N

'

4 1rE

and henc e nally in accordance with

,

3i n N

4E

the expression for the

F O UR TH LECTUR E

64

e ntropy S of the gas in a state of equilibrium wit h given values

fo r N V and E i s :
,

c onst

l og E

kN (

l og

V)

(20 )

T he additive constant contains terms i n N and m but not in

E and V
Th e determination of the entropy h ere carried out permits
now the specication directly of the complete thermodynamic
behavior of the g a s vi z of the equation of state and of the
values of the specic heats From the general thermodynamic
denition of entropy :
,

p dV

dE

dS

are O btained the partial differential quotients of S wit h regard

to E and V respectively :
dS

S
-

BE

6V

S
'

C onsequently wit h the aid of

,

6S

3 NV

dE

7
.

(2 1 )

and
6S
a
7

Th e

Ic N

(22)

second of these equations :

IcN T
P

contains the laws of B oyle G ay Lussac and Avogadro the latter

because the pressure depends only upon the number N and not
upon the constitution of t h e molecules W riting it i n the
ordinary form :
,

Rn T
P

E Q UAT I O N O F STATE

MO N ATOM I C G AS

FOR

65

where n denotes the numb e r of gram molecules or mols of the

3 29 and R the absolute gas constant :
gas referr e d to 0 2
,

erg
7
10
deg

w e obtain by comparison :
R

(23)

I f we de n ote the rati o of the mol numb e r t o the molecular

number by w or what i s the same thing the ratio of the
molecular mass t o the mol mass :
,

n
(O

and hence :
k

(O

(24)

From t h is if is given we can calculate the universal constant

k and conv e rsely
T h e equation (21 ) gives :
E gkN T
(25 )
,

N ow since the energy of an id e al gas is given by :

E

Anc T,
,

wherein
d e notes i n cal ories the h eat capacity at constant
volume of a mol A the mechanical equivalent of heat :
,

10

e rg

cal

it follows that :
3kN
0

and having regard to

,

2 An

we obtain :
3 R
2 A

(26)

F OURTH LECTUR E

66

the mol heat i n cal ories of any monatomic gas at constant volume
For the mol heat c p at constant pr e ssure we have from the
rst l aw of thermodynamics
.

Cp

a nd ,

Cv

therefore having regard t o

,

a known result for monatomic gases

T he mean kinetic energy L of a molecule is obtained from
.

T
l
e
g

(2 7 )

Yo u notice that we h ave derived all t h ese relations throug h the

i d e nt i c ati On

of the mechanical with the the rmodynamic e x

pression for the entropy and from this you recognize the fr u it
fulness of t h e method here proposed
B ut a method can rst demonstrate fully its usefulness w h en
we utili z e it not only t o derive laws whic h are already known
but when we a pply it i n domains for whose i nvestigation there
at present exist no other methods I n thi s connection its
application affords various possibilities T ake the case of a
m o natomic gas whic h i s not s ufciently attenuated to have t h e
properties of the ideal state ; there are h ere as pointed out by
J D van der W aals two things t o consider : (1 ) the nite size of
t h e atoms (2) the forces whic h act among the at oms T aking
account of t h ese involves a change i n the value of t h e probability
and in t h e energy of the gas a s well and s o far as can now b e
shown the corresponding change in the conditions for thermo
dynamic equilibrium leads t o an equation of state w h ic h agrees
wit h that of van der W aals C ertainly there is here a ric h eld
for further investigations of gr eater promise when experimental
tests of the equation of state exist i n larger number
,

'

EQUAT I ON O F STATE

FOR

M ONATOM I C G AS

67

important appl i cation of the theory has to do with

h e at rad i at i on with wh i ch we shall be occupi e d the coming
week We shall proceed then i n a s i m i lar w a y as h e r e and shall
b e able from the e xpr e ssion for th e e ntropy of radiat i on to d e ri ve
the thermodynam i c properties of radiant h e at
T oday we will r e fer bri e y to the tr e atment of polyatomic
gases I have pr e viously upon good grounds lim i ted the treat
ment t o monatomic molecules ; for up t o the present real dif
c u lt ie s appear t o stand i n the way of a generalization from
the principles employed by us t o include polyatom i c molecules ; i n
fact , if we wish t o be quite frank we must say that a satisfactory
mechanical theory of polyatomic gas e s has not yet b ee n found
C onsequently at present we d o not know t o what place i n the
system of theoretical physics t o assign the process e s within a

molecule the intra-molecular processes We are ob v iously con

fronted by puzzling problems A noteworthy and much dis
cussed beginning was i t i s true made by B olt z mann who intro
d u c e d the most plausibl e assumption that for i ntra -molecular
processes simple laws of the same kind hold as for the motion of
the molecul e s themselves i e th e g e neral equations of dynamics
I t is easy then i n fact t o proceed to the proof that for a mona
tomic gas the molecular h e at
must b e greater than 3 and that
cons e quently since th e diff e rence c p
e
is always equal to 2
the ratio is
Another

.
,

conclusion i s completely conrmed by experience B u t th i s

in itself do e s not conrm the assumption of B oltzmann ; for
indeed the same conclusion is r e ached very simply from the
assumption that there exists intra -molecular energy whic h
increases wit h the temperature For then the molecular heat
of a polyatomic gas must be greater by a corresponding amount
than that of a monatomic gas
N e verth e l e ss up to this p o i nt th e B olt z mann theory never l e a ds

T his

F OUR TH LECTURE

68

to contradiction with experience B u t s o soon as one seeks to

draw special conclus i ons conc e rning the magnitud e of the specic
heats ha z ardous dif culti e s arise ; I will ref e r t o only one of them
I f one assumes the H amilt onian equations of mechanics as
applicable t o intra -molecular motions he arrives of necessity at

the law of uniform distribution of energy which asserts that

under certain conditions not essential t o consider here i n a
thermodynamic state of equilibrium t h e t otal energy of th e gas
is distributed uniformly a mong all the individual energy phases
corresponding t o t h e i nd e pend e nt variables of state or as
one may briey say ; the same amount of energy i s associated
wit h every independent variable of state Accordingly the
mean energy of motion of the molecules %lc T corresponding t o a
given direction i n space is the same as for any other direction
and moreover the same for all t h e di ff erent kinds of molecules
and ions ; also for all suspended particles (dust ) in the gas of
w h atever size and furthermore the same for all kinds of motions
of the constituents of a molecule relative t o its centroid I f
one now reects that a molecule commonly contains s o far as
we know quite a large number of different freely moving
constituents certainly that a normal molecule of a mon
atomic gas e g mercury possesses numerous freely moving
electrons then i n accordance wit h the law of uniform energy
distribution the intra-molecular energy must constitute a much
larger fraction of the whole specic heat of the gas and therefore
c p /c
must turn out much small e r than is consistent wit h the
measured values
T hus e g for an atom of mercury in
accordance wit h the measured value of c p /c
no part
whatever oft he heat added may be assigned t o the intra -molecular
energy B oltzmann and others in order t o eliminate this con
t ra di c t i o n have xed upon the possibility t h at within t h e time
of observation of the specic heats t h e vibrations of t h e con
st it u e nt s (of a molecule ) do not change appreciably wit h respect
to one anot h er and come later with their progressive motion so
S lowly into heat equilibrium that this process is no l onger capable
.

EQUAT I ON O F STATE

FO R

M ONATOM I C GA S

69

of detection thro u gh observation Up to now no such d e lay in

the establishment of a state of equ i librium has been observed
Perhaps it would be productive of results if i n d e licate measure
ments special attention were paid the question as t o w h ether
observations which take a l onger time lead t o a gr e ater value of
the mol -heat or what com e s t o the sam e thing a smaller value
of c p /c than observations lasting a shorter time
I f one h a s been made mistrustful through these considerations
concerning the applicability of the law of un i form energy d i s
t ri bu t i o n to intra -molecular process e s the mistrust is acc e ntuated
upon the inclusion of the laws of heat radiation I S hall make
mention of this in a later lecture
Wh en we pass from stable atoms t o the unstable atoms of
radioactive substances th e principles following from the kinetic
gas theory l ose their validit y compl e tely
For the striking
failure of all attempts t o nd any inuence of temperature
upon radioactive phenomena S hows us that an application here of
the law of uniform energy distribution is certainly not warranted
I t will therefore be safest meanwhile t o offer no denite con
wit
h
regard
t
o
the
nature
and
the
la
w
s
of
these
note
u
re
s
c
t
e
j
worthy phenomena and to l e ave this eld for further dev e lopment
to e xp e rimental r e search alone which I may s a y with every
day throws new light upon the subj ect
.

v,

F I F T H L E C T UR E
HEAT R AD I AT I O N

E LECTRODYN AM I C T HEO R Y

week I end e avored t o point out that we nd in the

atomic theory a Complete explanation for the whole content of
the two laws of thermodynamics if we with B oltzmann dene
the entropy b v the probability and I have further shown i n the
example of a n Ide al monatomic gas how t he calculation of the
probability without any additional special hypothesis enables
us n ot only t o nd the properties of gases known from ther
m o d yn a m i c s but als o t o r e ac h conclusions whic h lie essen
T hus e g
t i a lly b eyond those of pure thermodynamics
the law of Avogadro i n pure thermodynamics is only a d e
while in the kinetic the ory it i s a necessary c o nse
ni t i o n
-heat of a gas is
furthermore
the
value
of
c
the
mol
n
u
e
c
e
;
q
completely undet e rmined by pure thermodynamics b ut from the
kinetic theory it is of equal magnitude for all monatomic gases
and i n fact equal t o 3 corresponding t o our experimental
knowledge T oday and t omorrow we shall b e occupied wit h
the application of the theory to radiant heat and it will appear
that we reach i n this appar e ntly quite isolated d omain con
elusions which a thorough test S hows are compatible wit h e x
magnetic
N
aturally
we
take
a
s
a
basis
the
electro
r
i
e
e
n
c
e
p
theory of heat radiation whic h regards the rays as electro
magnetic wav e s o f the same kind as light rays
We shall utili z e the time t oday i n dev e loping in bol d outline
the important consequences which foll ow from the electro
magnetic theory for the characteristic quantities of heat radiation
and t omorrow seek t o answer throug h the calculation of the
entropy the question conc e rning the dependence of th e se quan
Last

v,

70

HEAT RAD I A TI ON

ELECTRODYNAM I C THEORY

tities upon the temperatur e as w as done last week for ideal

gases Above all we are concerned her e with th e d e t e rmination
of those quantities which at a ny place i n a medium traversed
by heat rays d e termine the state of the radiant heat The state
of rad i ation at a giv e n p lace w i ll not be r e presented by a vector
which is determined by three components ; for the e nergy owing
i n a given direction i s qu i te independent of that owing i n any
other direction I n order t o know the state of radiation we
must b e able t o specify moreover the e nergy which i n the tim e
dl ows through a surface element do for ev e ry direction in
space T his will be proportional t o the magnitude of do to
the time dt and t o the cosine of the angl e 6 which the direction
considered makes wit h the normal to do B ut the quantity to
b e m ul tiplied by do o di c o s 6 will not be a nite quantity ;
for since the radiation through any point of do passes i n all dirce
tions therefore the quantity will also depend upon the magnitud e
of the solid angle d 9 which we shall assume a s the same for all
points of do I n this manner we obtain for th e e n e rgy which i n
the time dt ows throug h the surface elem e nt do in the direction
of the elementary cone d 9 the expression :
,

K da dt

cos

o d9

(28 )

K is a positive function of p la c e of time and of direction and is

for unpolarized light of the following form :
,

R dv

wh e re v denotes the frequ e ncy of a color of wave length

whose velocity of propagation is q :

(2 9 )
A and

1
x

and If denotes the corr e spond i ng intensity of spectral radiation

of the plan e polar i ze d light
,

F I FTH LECTUR E

72

From the value of K is to b e found the space density of radiation

i e the energy of radiation contained in unit volume Th e
6
point 0 in question forms the centre of a sphere whose radius r
we take s o small that in the distance r no appreciable absorption
of radiation takes place Then eac h element do of the surface
of the sphere furnishes by virtue of the radiation traversing the
same the following contribution t o the radiation density at 0 :
,

da -dt
2

K -d fl

dS2

do -K
2

For the radiation cone of s olid angle d proceeding from a point

of do i n the direction toward 0 has at the distance r from do the
2
cross section r df2 and the energy passing in the time dt through
this cross-section distributes itself along the distance t
By
integration over all of the surface elements do we obtain the
total space density of radiation at 0 :
.

Z
'

K do,

wherein d 9 denotes the solid angl e of an elementary cone whose

verte x is 0 For uniform radiation we obtain :
.

m
q

Sada

(30 )

Th e production of radiant h eat is a consequence of the act of

emission and its destruction is the result of absorption B oth
processes emission and absorption h ave their origin only in
material particles atoms or electrons not at the geometrical
bounding surface ; although one frequently says for t h e sake of
brevity that a surface el e ment emits or absorbs I n reality a
surface e lem en t of a b o dy i s a place of entrance for the radia
tion falling upon the b ody from without and whic h i s t o b e
absorbed ; or a place of exit for the radiation emitted from
within the body and passing through the surfac e in the outward
.

HEAT

R AD I A TI ON

ELECTRODYNAM I C THEORY

d i r e ct i on T h e capacit y f o r e m i ssi o n a nd th e capac i ty for

abs o rpt i on of an e l e m e nt o f a body d e p e nd only upon its o w n
condit i on and not upon that of th e surr o und i ng el e m e nt s If
therefor e as w e shall assume i n what follo w s the state O f th e
body vari e s only with the t e mperature th e n th e capacity for
emission and th e capacity for abs orpt i on of the b ody will als o
vary only with the temperatur e T h e d e pend e nc e upon the
t e mperature can of course b e di ff er e nt for each wa v e l e ngth
We shall now introduce that r e s u lt follo w i ng from the s e c
ond law of th e rmodynamics which will serve us as a basis
i n all subsequent considerations : a syst e m of bodies at r e st
of arbitrary nature form and position wh i ch is surround e d by a
x e d shell impervious t o heat pass e s i n the course of time from
an arbitrarily chosen initial s t at e to a perman e nt stat e i n which
the temperature of all bod i e s of the syst e m is the same
T his is the thermodynamic state of equilibrium i n whi c h th e
entropy of th e system among all those values which it may assume
compatible wit h the t otal energy speci e d by the i nitial condi
tions has a maximum value Le t us now apply this law t o a
single homogeneous isotropic medium whic h is of gr e at e xt ent
in all directions of space and which as i n all cases subsequ e ntly
consider e d is surround e d by a xed shell perf e ctly r e ecting as
regards heat rays T h e medium possesses for each frequency 1
of the heat rays a nite capacity for emission and a nite capacity
for absorption Le t us consider now such reg i ons of the medium
as are very far removed from the surface H e re the inuenc e
of the surface will be i n any case vanishingly small because n o
rays from the surface r e ach these regions and on account of th e
homog e n e ity and isotropy of the m e dium we must conclude that
the heat radiation is i n thermodynamic equilibrium everywhere
and has the same properti e s in all dir e c t i ons s o that If th e
specic intensity of radiation of a plane polarized ray i s ind e
p e ndent of the fr e qu e ncy V of th e a z i muth of polari z ation of the
d i r e ction of th e ray and of l ocation T hus th e r e will correspond
to e ach di ve rging bundle of rays i n an e l e m e ntary cone d 9
.

F I FTH LECTU R E

74

proceeding from a surface element do a n exactly equal bundle

oppositely directed within the same elemental cone converging
toward the surface element T his law retains its validity a s a
simple consideration shows right up t o the surface of the medium
For i n thermodynamic equilibrium eac h ray must possess
exactly the same intensity as that of the directly opposite ray
otherwise more e nergy would ow i n one direction than in
Le t u s x our attention Up o n a ray
t h e O pposite direction
proceeding inward s from the surface this must h ave the
sam e intensit y a s that of the d irectly opposite ray coming
from within a nd from this it follows immediately that the
state of radiation of the medium at all points on t h e surface is
t h e s ame as that within Th e nature of the bounding surface
and t h e spacial e xtent of t h e medium are immaterial and in a
stationary state of radiation R is completely determined by t h e
nature of t h e medium for eac h temperature
T his law suffers a modication however i n t h e special case
t h at the medium is absolutely diat h ermanous for a denite
frequency 1
I t is then clear that the capacity for absorption
and also that for emission must b e zero because otherwise no
stationary state of radiation could e x ist i e a medium -emits
no color w h ic h it does not absorb B ut equilibrium can then o b
v i ou sly e x ist for every intensity of radiation of the frequency con
s i d e re d i e
if i s now undetermined and cannot b e found with
out knowledge of t h e initial conditions An important example of
this i s furnished by a n absolute vacuum w h ich is diat h ermanous
for all frequencies I n a complete vacuum t h ermodynamic
equilibrium can t h erefore exist for eac h arbitrary intensity of
radiation and for eac h frequency i e for eac h arbitrary dis
From a general thermodynamic
t rib u t i o n of the spectral energy
point of view t h is indeterminateness of the propert ies of t h ermo
dynamic states of equilibrium i s explained throug h t h e presence
of numerous different relative maxima of the entropy as in t h e
case of a vapor w h ic h is i n a state of supersaturation B ut
among all the di ff erent ma x ima t h ere i s a special ma x imum the
,

2.

HEAT RAD I AT I ON

ELECTRODYNAM I C THEORY

75

absolut e whic h i ndicates stabl e e qu i l i brium I n fact we shall

see t hat i n a diathermanous medium for each temperatur e th e r e
e x ists a quite denite i nt e nsity of radiati o n which i s d e sig
na t e d as the stable i ntensity of rad i ation of th e frequency V con
B u t for the pres e nt we shall assume for al l frequ e ncies
s i d e re d
a nite capacity for absorption and for e mission
We consid e r now t w o homogeneous isotropic m e dia in thermo
dynamic equilibrium s e parated from each other by a plan e
surface S ince the equilibrium will not be disturbed if one
imagines for the moment the surface of s e parati on between the
two substances t o be replaced by a surface quite non-transpar e nt
to heat radiation all of the foregoing la w s hold for eac h of the
,

FIRS T MEDIUM
'
I

a
.
,
l
I
I

d0

BOU DARY 8 URFAC E

I
I

iMEDIUM
RV

s ec o no

Fi g 1
.

two substances individually Le t the specic intensity of radi

ation of frequency V polari z ed i n any arbitrary plane within the
rst substance (the upper i n Fig
b e If and that within th e
second substance R (we S hall in general designate wit h a dash
Fr o m m y l ec tures u p on th e theor y o f hea t r a di a ti o n (Lei p i g J A B a rth )
wherei n are t o b e f o un d the d eta ils of t he ab ove somewh a t abbr evi a t ed
.

l l i

c a c u a t o ns

F I FTH LECTUR E

76

those quantities w hich r e f e r to the s e cond substance ) B oth

quantities If and i f ! besid e s d e p e nding upon the temp e rature
and the frequency dep e nd only upon the nature of the two s ub
stances and i n fact these valu e s of the intensity of radiation
hold quite up t o the b oundary surface between the substanc e s
and are th e refore independent of the properties of this surface
E ach ray fro m the rst medium i s split i nto two rays at t h e
boundary surface : the reected and the transmitted T he dirce
tions of these two rays vary according t o the angle Of inci
dence and the color O f the incident ray a nd i n addition the
intensity varies according t o its polarization I f w e denote
by p (the reection coefcient ) the amount of the reected
energ y of radiation and consequently by 1
p the amount of
transmitted energy wit h respect t o the incident energy t h en p
depends upon the angle of incidence upon the frequency and
upon t h e polarization of the i ncident ray S imilar remarks h old
for p the reection coefcient for a ray from the second
medium upon meeting t h e b oundary surface
N ow the energy of a monochromatic plane polari z ed ray of
frequency : proceeding from an element do of the b oundary
surface within the elementary cone d in a direction toward the
rst medium (see t h e feathered arrow at the left in Fig 1 ) is
for the time dl in accordance wit h (28 ) and
.

dt o do

cos

dS

R dv,

(3 1 )

where
d9

sin

6 d 6 dgo

(32)

energy is furnished by t h e two rays which approaching the

surface from the rst and t h e second medium resp e ctively are
r e ected and transmi tted respectively at the surface element do
in the s ame di rection (S e e the unf e ath e r e d arrows Th e surface
Th e rst ray pro
element do is indicated only b y the point
c e e d s in accordance wit h the law of r e ection within the s y m
m e trically drawn elementary cone d9 : the second approaches
the surface within t h e elementary cone
T his

HEAT RAD I AT I O N
dfl

ELECTRODYNAM I C THEORY

sin

(33)

wh e r e i n accordance wit h th e law of r e fract i on

,

so

77

sin

and

so

S in

(34 )

We now assume that the ray is either polarized i n the plane of

incidence or perp e ndicular to this plane and l i kew i se for the
two radiations out of whose e nergies it i s compos e d The radia
,

tion coming from the rst medium and reected from

tributes the energy :
do

dl

cos

do

d9 o E du,

con
(35 )

and the radiation coming from the s e cond medium and trans
m itt e d throug h do contributes the energy :
(1

o
) dt

do

cos

d fl

E du

(36)

quantities dt do V and d z are here written without the

acc e nt S ince they have the s a m e values i n both m e dia
Adding the e xpressions (35 ) and (36) and placing the s u m
equal t o the expression
we obtain :

T he

N ow

cos Mil li

(1

) cos

cos

i n accordance with
d z9

cos

cos

29

d dd

and further taking not e of (32) and

,

d9

cos

cos

d9

,2

and it follows that :

,2

p it y

(1
R
R

(1

!
V

,2

6 dQ

F I FTH LE CTUR E

78

I n the last equation the quantity on t h e l eft i s i ndependent

of the angle of i ncidence 6 and of the ki nd of polarization con
sequently the quantity upon the right side must also b e inde
pendent o f these quantities I f one knows t h e value of t h ese
quantities for a single angle of incidence and for a given kind of
polari z ation then t h is value i s valid for all angles of incidence
and for all polarizations N ow i n the particular case that t h e
rays are polari z ed at right angles t o t h e plane of i ncidence and
meet the b ounding surface at the angle of p olari z ation
,

=
0
p

and

= 0

Then

the expression on the right will be equal to 1 an d t h ere

fore it is i n general equal t o 1 and we h ave always :
,

9 8

Th e

(37 )

rst of these two relations whic h asserts that the coefcient

of reection is the same for b ot h s ides of the b oundary s urface
constitutes the s pecial expression of a general reciprocal la w
rst announced by H elmholz whereby the l oss of intensity which
a ray of given color and polarization s uffers on its pat h t h rough
any medium i n consequence of reection refraction a bsorption
and d i spersion is exactly equal t o the l oss of i ntensity whic h a ray
of corresponding intensity color a nd polarization s uffers i n
passing over the directly opposite path I t follows i mmediately
from this that the radiation meeting a b oundary s urface b e tween
two media i s transmitte d or re e cted equally well from b ot h
S ides for every color direction and polarization
Th e second relation
brings into connection t h e radiation
intensities originating i n b ot h substances It assert s that in
th e rmodynamic equilibrium t h e specic i ntensities of radiation
of a denite frequency i n b ot h media vary inversely as the square
of the vel ocities of propagation or directly a s the squares of the
refractive indices We may therefore write
,

(1

F0 . T) .

HEAT R AD I AT I ON

E L E CT RODYNA MIC THEORY

79

wher e i n F d e notes a universal function d e pending only upon v

and T the discovery of which is one of the chief problems of the
theory
Le t us x our attention again o n t h e case of a diathermanous
medium W e s a w above that i n a medium surrounded by a
non -transparent shell whic h for a given color is diathermanous
equilibrium can exist for any given intensity of radiation of this
color B ut it follows from the second law that among all the
intensities of radiation a denite one namely that corresponding
t o the absolute maximum of the total entropy of the system
must exist whic h characterizes the absolutely stable equilibrium
of radiation We now se e that this indeterminateness i s climi
mated by the last equation which assert s that in thermodynamic
z
equilibrium the product q if is a universal function For it
results immediately therefrom that there is a denite value of
If for every diathermanous medium whic h i s thus di ff erentiated
from a ll other values Th e physical meaning of t h is value is
derived directly from a consideration of the way i n whic h this
equation was derived : it i s that intensity of radiation which
exists in the diathermanous medium when it i s i n thermodynami c
equilibrium while in contact with a given absorbing and emitting
medium T he volume and the form of t h e second medium is
immaterial ; i n particular the volume may be taken arbitrarily
small
For a vacuum the most diathermanous of all media i n which
the velocity of propagation q
c is the same for all rays we can
therefore express the following law : The quantity
,

(38 )

T)

denotes that intensity of radiation whic h e x ists in any complete

vacuum when it is in a stationary state a s regards exchange of
radiation with any abs orbing and emitting substance whose
amount may be arbitrarily small T his quantity R regarded
as a function of V gives the s o-called normal energy spectrum
,

F I FTH LECTUR E

80

us consider therefore a vacuum surrounded by given

em i tting and absorbing b odies of uniform temperature T hen
in the course of time th e re is established therein a normal energy
radiation R corresponding t o this temperature I f n ow p b e
the reection coefcient of a wall for the frequency V t h en of
the radiation R falling upon the wall the part p R will b e re
e c t e d
O n the other hand if we designate by E the emission
coe f cient of the wall for the same frequency V the total radiation
proceeding from the wall will be :
Le t

p V Q V

1)

V,

since each bundle of rays possesses in a stationary state the

t e nsity R
From this it follows that :
,

in

p.

(39 )

i e the ratio of the emission coefcient E to the capacity for

absorption (1
p ) of a given substance i s the same for all
substances and equal t o the normal intensity of radiation for
e ach fr e quency (K ircho ff ) For the special case that p is equal
to 0 i e that the wall S h all be perfectly black we have :
.

V,

is the normal intensity of rad i ation is exactly equal to the

emission coefci e nt of a black body T h e r e fore the normal

radiation is als o called black radiation

Again for any given
body i n accordance with
we have :
that

i e t h e emission coefcient of a body i n general is smaller t h an

that of a black b o dy B lack radiation thanks t o W W ien and
O Lu m m e r has been made possible of measurement thro u gh
a small hole bored in the wall bounding the space considered
We proceed now t o the tr e atment of the problem of deter
mining the specic int e nsity R of black radiation in a vacuum
.

H EAT RAD I AT I ON

ELECTRODYNAM I C THEO R Y

81

as regards its dependence upon the fr e qu e ncy V and the temper

atur e T I n the treatm e nt of this probl e m it w i ll be necessary
to go further than we have pr e viously done into thos e processes
whic h condition the production and d e struction of he at rays ;
that is into the question regarding the act of emission and that
of absorption O n account of the compl i cated nature of t h ese
processes and th e di ffi culty of bringing some of the details into
connection with experi e nc e it is certainly quite out of the ques
tion to obtain in this manner any reliable r e sults if the foll owing
law cannot b e utili ze d as a d e pendabl e guide i n this d omain : a
vacuum surrounded by r e ecting walls i n whic h arbitrary
emitting and absorbing b odies are distributed i n any given
arrang e ment assum e s in the course of time the stationary state
of blac k radiation whic h i s completely determined by a single
parameter the t e mperature and which i n particular does not
depend u pon the number the properties and t h e arrangement of
the b odies I n the investigation of the prop e rti e s of the state
of black radiation t h e nature of the bodies which are supposed
to be i n the vacuum is therefore quite immaterial and it is cer
t a i nly immaterial whether such bodies actually exist anywhere
in nature so long as th e ir existence and their properties are
compatible throughout with the laws of electrodynamics and of
thermodynamics As soon as it is possible t o associate with
any given special kind and arrangement of emitting and absorbing
bodies a state of radiation i n the surrounding vacuum which
is characterized by absolut e stability then this state can be no
other than that of black radiation M aking use of the freedom
furnished by this law we choose among all the emitting and
absorbing systems conceivabl e the most simple namely a single
oscillator at rest consisting of two poles charged wit h equal
quantities of electricity of opp osite sign which are movable
relative t o each other in a x e d straight line the axis of the
oscillator The stat e of th e oscillator is complet e ly d e t e rmined
by its moment f (t) i e by th e product of th e e l e ctric charg e of
the pole on the positiv e side of th e axis into th e d i stance bet w een
.

F I FT H LE CTU R E

82
t h epoles ,

and by its differential quotient with regard to the t i me :

d

Th e

energy of t h e oscillator i s of the following simple form :

1 9

(4 0 )

wherein K and L denote positive constants whic h depend upon

the nature of the oscillator in some manner into whic h we need
not go further at t h is time
I f in t h e vibrations of the oscillator the energ y U remain a b
s o lu t e ly constant we s h oul d have : d U
0 or :
,

Kf (t)

i a)

0.

and from this there results as a general solution of t h e differential

equation a pure periodic vibration :
,

cos (27rVot

wherein 0 and 6 denote the integration constants and

number of vibrations per unit of time :
V0

V0

the

(4 1 )

27

S uc h

an oscillator vibrating periodically wit h constant energy

woul d neither be inuenced by the electromagnetic eld s u r
rounding it nor woul d it e x ert any external actions due to radi
ation It coul d therefore have no s ort of inuence on the h eat
radiation In the surrounding vacuum
I n accordance wit h the theory of M a x well t h e energy of
v ibration U of t h e oscillator b y no means remain s constant i n
general but a n oscillator by virtue of its vibrations sends out
spherical waves i n all directions into t h e surrounding el d and
in accordance with the principle of conservation of energy if n o
actions from without ar e e x erted upon the oscillator there must
,

HEAT R AD I AT I O N

E LECT R ODY N AM I C THEO R Y

83

necessarily be a loss in the energy of vibration and therefore a

damping of th e amplitude of vibration is i nvolved I n o rder to
nd the a mount of this damping we calculate the quantity of
energy w h ic h ows out throug h a S pherical surface wit h the
oscillator at the center i n accordance with the law of Poynting
H ow e ver we ma y not place the energy owing outwards in
accordance with this law throug h the spherical surface in an
innitely small interval of time dt equal t o the energy radiated
in the same time interval from the oscillator For i n general
the electromagnetic energy does not always ow i n the out
ward direction but ows alter nately outwards and inwards and
we S houl d obtain i n thi s manner for the quantity of the radia
t i on out wards values which are alternately positive a nd nega
tive and whic h a lso depend essentially upon the radius of the
supposed sphere i n suc h manner that they increase toward
innity with decreasing radius which is opposed t o the funda
mental conception o f radiated energy T his energy will m o r e
over b e only found ind e pendent of the radiu s of t h e S p he r e
when we calculate the total a mount of energy owing outwards
throug h the s urface of the s phere not for the time element
I f the vibrations are purely
di but for a s u i c i e nt ly large time
periodic we may choose for the time a period ; if t h is i s not
the case which for the sake of generality we must h ere assume
it is not possible t o specify a priori any more general crit e rion
for the least possible necessary magnitude of t h e time than t h at
which make s the energy radiated essentially independent of the
radius of the supposed sphere
I n this way we succeed in nding for t h e energy emitted from
the oscillator in t h e time from t to t Q the following expression :
,

30

f (t) dt

I f now the oscillator be in an electromagnetic eld whic h has t h e

electric component 63 at the oscillator in the direction of it s a xis
,

F I FTH LECTUR E

84

then the energy absorbed by

the

oscillator in the same time

Rf
H ence

is :

dt

the principle of conservation of energy is expressed in

the following form :
,

dU

dt
Th is

3c

dt

6 f
2

'

equation t ogether with the assumption that the constant

,

4 71

11 0

(4 2)

3c L

is a small number leads t o the foll owing linear di ff erential equa

tion for the vibrations of the oscillator :
,

'

Kf

Lf

(43)

I n accordance wit h what precedes i n so far as t h e oscillator is

e x cited into vibrations by an external eld (5 one may designate
it a s a resonator whic h possesses t h e natural period V 0 and the
small l ogarithmic decrement o Th e same equation may be
obtained from the electron theory but I h ave considered it an
advantage t o derive it i n a m anner i ndependent of any h ypothesis
concerning the nature of the resonator
N ow let the resonator be i n a vacuum lled wit h stationary
blac k radiation of specic intensity R
H o w then does the
mean energy U of the resonator i n a state of stationary vibration
depend upon t h e specic intensity of radiation R with t h e natural
period DO of the corresponding color ? It is this question which
we have still t o consider today It s answer will b e found by ex
pressing o n t h e one h and t h e energy of t h e res onator U and on
the ot h er h and the int e nsity of radiation R ; by means of the
component (i of t h e e lectric e l d exciting the resonator N ow
ho wever complicated this quantity may be it is capable of
,

2,

H EAT R AD I AT I O N

E LECT R O DYNAM I C T H E O R Y

85

development i n any case for a very large time interval from

t
0 to t
E i n the Fourier s series :
,

(S

=w

=1

cos

2m

(44 )

on

3:

and for this same time interval E the moment of the resonator
in the form of a Fourier s series may be calculated as a function
of t from the linear di fferential eq u ation
Th e initial
condition of the resonator may be neglected if we only consider
such times t as are sufciently far removed from the origin of
time t
0
I f it be now recalled that in a stationary state of vibration
the mean energy U of the resonator is given in accordance with
by :
(4 1 ) and

Kf

30

it appears a l t e r substitution of the value of f obtained from the

differential equation (4 3) that :
U

30
64 7

s ome,

(4 5 )

for all the series of

wherein O denotes the mean value of
numbers n which lie in the neighborhood of the value
i e
1
for which 1 0$ is approx imatel y
N o w let us consider on the other hand the intensity of black
radiation and for this purpose proceed from the space density
of the total radiation I n accordance with
this is :

no

@5
7
1

a dv

c:
(
7
8,

o:

of

(4 6)

and therefore since the radiation is isotropic in accordance with

,

8 7r

86

LE CT U R E

FI FT H

I f we write An /$ on the l eft instead of

number we get :

d z ,

where An i s a large

and obtain then by

spectral
3
V0

division of this equation :

"

87

no (An lz)

Z
" g

and if we introduce again the mean value

,

On

n o- (

On 0

lz)

we then get :
Q
By

30 %
vo

2
-

6 4 71

0 11 0

'

c omparison with (4 5 ) the relation sought is now found :

V0

U,

(4 7 )

which is striking on account of its simplicity and i n particular

because it is quite independent of the damping constant a of the
resonator
T his relation found i n a purely electrodyna mi c manner
between the spectral intensit y of black radiation and the energy
of a vibrating resonator will furnish us in the next lecture with
the aid of thermodynamic considerations the n ecessary means of
attack i n deriving the temperature of black radiation together
with the distribution of energy i n the normal spectrum
,

S I XT H LE C T UR E

H EAT R AD I AT I O N

STAT I S T I CA L T H E O R Y

Following the preparatory considerations of the last lecture

we shall treat today the problem which we have come to recognize
as one of the most important i n the theory of heat radiation :
the establishment of that universal function which governs the
energy distribution i n the normal spectrum The means for the
solution of this problem will be furnished us through the c a lc u
lation of the entrop y S of a resonator placed i n a vacuum lled
wit h black radiati o n and thereby excited into stationary vibra
tions I ts energy U is then connected with the corresponding
specic intensity 9 and its natural frequency 1 in the radi ation
of the surrounding eld through equation
.

(4 8 )

W hen S is found as a function of U the temperature T of the

resonator and that of the surrounding radiation will be given by :
,

d8

dU

(4 9 )

and by elimination of U from the last two equations we then

nd the relationship among
T and V
I n order to nd the entropy S of the resonator we will utilize
the general connection betwee n entropy and probability which
we have extensively discussed in the previous lectures and inquire
then as to the existing probability that the v ibrating resonator
possesses the energy U I n accordance with what we have seen
in connection with the elucidation of the second law through
,

87

88

LE CT U R E

S IX T H

atomistic ideas the second law is only applicable to a physical

system when we consider the quantities which determine the
state of the system as mean values of numerous disordered
individual values and the probability of a state is then equal
to the number of the numerous a priori equally probable com
Ac
p le x i o n s which make possible the realization of the state
c ord i ng ly
we have to consider the energy U of a resonator
placed i n a stationary eld of black radiation as a constant mean
value of many disordered independent individual values and
this procedure agrees with the fact that every measurement of
the intensity of heat radiation is extended over an enormous
number of vibration periods Th e entropy of a resonator is
then to be calculated from the existing probability that the energy
of the radiator possesses a denite mean value U within a certain
time interval
I n order to nd this probability we inquire next as to the
existing probability that the resonator at any xed time pos
sesses a given energy or i n other words that that point (the
state point ) w h ich through its coordinates indicates the state of

the resonator falls in a given state domain

At the conclusion
of the third lecture (p 5 7 ) we saw in general that this proba
b ilit y i s simply measured through t h e magnitude of t h e cor
responding state domain :
,

d go

dip)

in case one employs as coordinates of state the general coordinate

N o w i n general the
g0 and the corresponding momentum
energy of the resonator i n accordance with
is :
,

%Kf

%Lf

2
.

I f we choose f as the general coordinate g0 and put therefore

x is equal
t
then
the
corresponding
impulse
o
l
s
f
,

eU
6f

HEAT R AD I AT I O N

S TAT I ST I CA L T H E O R Y

and the energy U expressed as a function of

%K go

go

89

and ilz is :

gI

I f now we desire to nd the existing probability that the energy

of a resonator shall lie between U and U + A U we have to
-plane
calculate the magnitude of that state domain i n the (go
which i s bounded by the curves U
const and U+A U= const
T hese two curves are similar and similarl y placed ellipses and
the portion of surface bounded by them i s equal t o the difference
of the areas of the two ellipses The areas are respectively U/ v
and (U A U) / V ; consequently the magnitude s ought for the
state domain is : A U/ V Le t us now consider the whole state
plane s o divided into elementary portions by a large number of
ellipses suc h that the annular areas between consecutive ellipses
are equal to each other ; i e so that :
,

AU

const

W e thus obtain those portions A U of the energy which correspond

to equa l probabilities and which are therefore to be designated
as the energy elements :
6

AU

hV

(50 )

I f the determination of the elementary domains i s effected in

a manner quite similar t o that employed in the kinetic gas the ory
there exist with respect to the relationships there found very
notable di ff erences I n the rst place the state of the physical
system considered here the resonator does not depend as there
upon the coordinate s and the velocities but upon the energy
only and this circumstance necessitates that the entrop y of a
state depend not upon the distribution of the state quantities
but only upon the energy U A further difference
go and I}
consists in this that we have t o do i n the case of molecules with
s pacial mean values but in the case of radiation with mean values
,

S I X TH LECTURE

90

as regards time B u t this distinction may be disregarded when

we reect that the mean time value of the energy U of a given
resonator is obviously identical with the mean space value at a
given instant of ti me of a great number N of similar resonators
distributed i n the same stationary eld of radiation Of course
these resonators must be placed su f ciently far apart in order
not directly to inuence one another T hen the total energy of
all the resonators :
.

NU

UN

(5 1 )

is quite irregularly distributed among all the individual resonators

and we have referred back the disorder as regards time to a
disorder as regards space
W e are now concerned with the prob ability W of the state
determined by the energy UN of the N resonators placed in the
same stationar y el d of radiation ; i e with the number of
individual arrangements or comple x ions w hi ch correspond t o the
distribution of energy UN among the N resonators With this
in view we sub divide the given total energy UN into its elements
e so that :
,

(5 2)
T hese P

energy elements are to be distributed i n every possible

manner among the N resonators Le t us consider then the
N resonators to be numbered and the gures written beside
one another i n a series and i n such manner that the number
of times each gure appears i s equal t o the number of energy
elements which fall upon the corresponding resonator T hen
we obtain through such a number series a representation of a
xed complexi on i n which with each individual resonator there
is associated a denite energy For example if there are N
6 energy elements present then one of
4 resonators and P
the possible complex1 ons l s represented by the number series
.

1 1 3 3 3 4

which asserts that the rst resonator contains two the second
,

0,

H EAT R AD I AT I O N

S TAT I S T I CA L T H E O R Y

the third 3 and the fourth 1 energy element T he totality of

numbers i n the series i s 6 equal t o the number of the energy
elements present Th e arrangement of gures i n the series i s
immaterial for any compl exion since the mere i nterchange of
gures does not change th e energy of a given resonator Th e
number of all the possible different complexions is therefore
equal to the number of possible combinations with repetition
of 4 elements with 6 classes :
.

M+

o r,

l
6

9!

nm!

mm

8 4,

in our general case the probability sought is :

n!
(N +

DW !
(N

W e obtain therefore for the entropy S N of the resonator system

i n accordance wit h equation
since N and P are large
numbers
,

SN = k b g

-P

(N +

)!

1W P I

and with the aid of S terling s formula

SN

k { (N + P )

l og (N +

P)

P lo g P }

N log N

I f in accordance with
we now write UN / e for P N U for UN
i n accordance with
and by for e i n accordance with
we obtain after an easy transformation for the mean entropy
of a single resonator :
,

S k

U % I;
m
w

as the solution of the problem in hand

W e will now introduce the temperature T of the resonator
and will express through T the energy U of the resonator and
also the intensit y R of the heat radiation related to it through a
.

,.

S I X TH LECTU R E

92

stationary state of energy exchange For this purpose we utiliz e

equation (4 9 ) and obtain then for the energy of the resonator :
.

In!

U
e

h v [k T

I t is to b e observed that we have not here to d o with a uniform

distribution of energy (cf p 68 ) among the various resonators
For the specic intensity of the monochromatic plane polarized
ray of frequency v we have i n accordance with
.

Il l/
y

1
6

h v / lc T

(53)

T his

expression furnishes for each temperature T the energy

distribution i n the normal spectrum of a black body A com
parison with equation (38 ) of the last lecture furnishes us then
W ith the universal function :
.

h v / Ic T

I f we refer the Specic intensity of a monochromatic ray not to

the frequency u but as i s commonly d one i n experimental physics
to th e wave length ) then since between the absolute values of
d v and d>
\ the relation exists :
,

x,

t ll

we

obtain from

the relation :
e

ch

/ k AT

as the intensity of a monochromatic plane polarized ray of wave

length ) w h ich i s emitted normally t o the surface of a black
b ody in a vacuu m at tem p erature T For small values of AT
x

HEAT RAD I AT I O N

STAT I ST I CAL THEO R Y

93

(5 4 ) reduces to :
2

EA

12
e

which expresses W ien s D isplacement La w

AT on the other hand there results from

Fo r large values of

EA

c kT

(5 6)

a relation rst established by Lor d R ayleigh and which we may

here designate as the R ayleigh La w of R adiation
From equation
taking account of
we obtain for the
space density of black radiation i n a vaccuum :
.

4 8 7Th
c

T,

wherein
1
a

The S tefan -Boltzmann

law i s hereby expressed I n accordance

with the measurements of K u rlb a u m we have the constant
.

4
7F 6

48 1
a

erg

10
C

deg

For that wave length km which corresponds i n the spectrum

of black radiation to the maximum intensity of radiation E x
we have from equation
dx

C arrying

out the di ff erentiation we get after putting for brevity

,

ch

kM T
Th e

[3

{j

1 0

root of this transcendental equation is :

B

S I X TH LECTUR E

94

and ) m c h/k b i s a constant (Wien s

I n accordance with the measurements of

D isplacement La w)

O Lu m m e r

and

Pri ng sh e i m ,

cm

deg

From this there follow the numerical values

k

10

erg

- 16

deg

and

27

10

erg sec

value found f or k easily permits of the sp ecication numeric

ally i n the C G S system of the general connection between
entrop y and probability as expressed through the universal
equation
T hus quite i n general the entropy of a physical
system is :

Th e

1 6

10

log W

I n the application to the kineti c gas theory we O btain from

equation (24 ) for the ratio of the molecular mass to the mol mass :

00

i e to one mol there corresponds 1 / oo

where it i s supposed that the mol of oxygen
.

o 1 023 molecules

Accordingly ,

the number of molecules contained i n 1 cu cm of

an ideal gas at 0 C els and at atmospheric pressure is :
.

10

19
.

mean kinetic energy of the progressive motion of a molecule

at the absolute temperature T 1 in t h e absolute C G S system
in accordance with
is :

Th e

3k

I n general the mean kinetic energy

,

- 16

10
O

progressive motion of a

H EAT R AD I AT I ON

STAT I ST I CAL T H E O R Y

95

molecule is expressed by the product of this number and the

absolute temperature T
Th e elementary quantum of electricity or the free electric
charge of a monovalent ion or electron i n electrostatic measure is :
.

10

965 8

00

10

T his

result stands i n noteworthy agreement with the results of

the latest direct measurements of the electric elementary quantum
made by E R utherford and H Geiger and E R egener
E ven if the radiation formul a (5 4 ) here deri v ed had shown itself
as valid with respect to all previous tests the theory would still
require an extension as regards a certain point ; for in it the
physical meaning of the universal constant k remains quite
unexplained All previous attempts to derive a radiation formula
upon the basis of the known laws of electron theory among which
th e the ory of J H J eans is t o be considered as the most general
and exact have led t o the conclusion that h is innitely small
s o that therefore the radiation formula of R ayleigh possesses
general validity but i n my opinion there can be no doubt that
this formula l oses its validity for short waves and that the pains
1
which J eans has taken t o place the blame for the contradiction
b etween theory and experiment u pon the latter are unwarranted
C onsequently there remains onl y the one conclusion that
pre v iou s electron theories suffer from an essential incompleteness
which demands a modication but how deeply this modication
should go int o the structure of the theory i s a question upon
which views are still widely divergent J J T hompson inclines
to the most radical view as do J Larmor A E instein and
with him I Stark who even believe that the propagation of
electromagnetic waves i n a pure vacuum does not occur precisely
in accordance with the M axwellian eld equations but in
denite energy quanta 121
I am of the opinion on the other
hand that at present it is not necessary to proceed in so rev olu
In t ha t t h e w alls us ed i n t h e m eas u re m e nt s o f h o ll o w s p a c e r ad i at i o ns
m u s t b e d i at h erm ano u s f o r t h e s h ort es t waves
.

2.

SI X TH LE CTU R E

96

a manner and that one may come successfully through by

seeking the signicance of the energy quantum hv solely i n
the mutual actions with which the resonators inuence one
1
another
A denite decision with regard to these important
questions can only be brought about as a result of further
experience
I t i s m y i nt e nt i on to g i ve a c om p l e t e pr es e nt a t i on o f t h es e re la t i on s i n
V o l u m e 3 1 o f t h e Ann al e n d er P h ys ik

t i o na ry

S E V E N T H LE C T URE
G ENE R AL

D YNAM I CS

PR I NC I P LE

OF

LEAST A CT I O N

S ince I began three weeks ago today to depict for you the

present status of the system of theoretical physics and its

probable future development I have continually sought to
bring out that in the the oretical physics of the future the most
important and the nal division of all physical processes woul d
likely be into reversible and irreversible processes I n succeeding
lectures with the aid of :the calcul us of probability and with the
introduction of the hypothesis of elementary d isorder we have
seen that all irreversible processes may be considered as reversible
elementary p rocesses : i n other words that irreversibility does
not depend upon an elementary property of a physical process
but rather depends upon the ensemble of numerous disordered
elementary processe s Of the same kind each one of which i n
dividually is completely reversible and upon the introduction
of the macroscopic method of treatment From this standpoint
one can sa y quite correctly that in the nal analysis all processes
in nature are reversible T hat there is herein contained no con
t ra d i c t i o n to the principle regarding the irreversibilit y of processes
expressed i n terms of the mean values of elementary processes
of macroscopic changes of state I have demonstrated fully in
the third lecture Perhaps it will be appropriate at this place
to interject a more general statement W e are accustomed i n
physics to seek the explanation of a natural process by the method
of d iv i sIO n of the process into elements W e regard each com
plicated process as composed of simple elementary pr ocesses
and seek to analyse it through thinking of the whole as the sum
of the parts T his method however presupposes that through
,

97

SEVENTH LECTUR E

98

this division the character of the whole is not changed ; i n some

what S i milar manner each measurement of a physical proce ss
presupposes that the progress of the phenomena is not inuenced
by the introduction of the measuring instrument e ha y e
here a case i n which that supposition i s not warranted and where
a direct conclusion with regard t o the part s applied to the w hol e
leads to quite false results I f we divide an irreversible process
into its elementary constituents the disorder and along with it
the irreversibility vanishes ; an irreversible process must remain
beyond the understanding of anyone who relies upon the funda
mental law : that all properties of the whole must also be recog
ni z a b le i n the parts
I t appears t o me as though a similar dif
c u lt y presents itself i n most of the problems of intellectual life
N o w after all the irreversibility i n nature thus appears i n a
certain sense eliminated it i s an illuminating fact that general
elementary dynamics has only to do with reversible processes
T herefore we shall occupy ourselves i n what follows with re
v e rsi bl e processes exclusively
T hat which makes this procedure
s o valuable for the theory is the circumstance that all known
reversible processes be they mechanical electrodynamical or
thermal may be brought together under a singl e principle which
answers unambiguously all questions regarding their behavior
This principle is not that of c onservation of energy ; this holds it
is true for all these processes but does not determine unam
b iguo u sly thei r behavior ; it is the more comprehensive principle
of l east action
Th e principle of least action has grown upon the ground of
mechanics where it enjoys equal rank and regard with numerous
other principles ; the principl e of d Ale m b e rt the principle of
virtual displacement Gauss s principle of l east constraint the
Lagrangian E quations of the rst and second kind
All these
principles are equivalent to one another and therefore at bottom
are only di ff erent formularizations of the same laws ; sometimes
one and sometimes another is the most convenient to use Bu t
the principle of least action has the decided advantage over all
.

GENERAL DYNAM I CS

P R I NC I P LE O F LEAST ACT I ON

99

t he

other principles mentioned i n that it connects together i n a

singl e equation the relations between quantities which possess
not only for mechanics but als o for electrodynamics and for
thermodynamics direct signicance namely the quantities :
space time and potential T his is the reason why one may
directly apply the principl e of least action to processes other
than mechanical and the result has shown that such applica
tions as well i n electrodynamics as i n thermodynamics lead to
the appropriate laws holding i n these subjects S ince a re p re
s e nt a t i o n of a unied system of theoretical physics such as we
have here i n mind must lay the chief emphasis upon as general
an interpretation as possible of physical laws it i s self evident
that i n our treatment the principl e of least action will be called
upon t o play the principal rOle I desire now t o show how it is
applied i n simple i ndividual cases
Th e general formularization of the principle of least action in
the i nterpretation given t o it by Helmholz i s as follows : among
all processes which may carry a certain arbitrarily given physical
system subject to given e xt ernal actions from a given i nitial
position into a given nal position i n a given time the process
which actually takes place i n nature i s that which i s distinguished
by the condition that the i ntegral
,

(6H

A) dt

(5 7 )

o,

wherein an arbitrary displacement of the independent coordinates

(and velocities ) i s denoted by the sign 5 and A denotes the
innitel y small increase i n energy (external work ) which the
system experiences i n the displacement 6 Th e function H
is the kinetic potential When we speak here of the positions
the coordinates and the velocities of the conguration we under
stand thereby not only those special ones corresponding to me
c h a ni c a l ideas but also all the s o -called generalized coordinates
with the quantities derived therefrom ; and these may represent
equally well quantities of electricity volumes and the like
,

S E V ENTH LECTUR E

1 00

I n the applications which we shall n o w make of the pri nciple

of least action we must rst decide as t o whether the gener
a li z e d coordinates which determine the state of the system con
s id e re d are present i n nite number or form a continuous i nnite
manifold W e shall distinguish the examples here cons idered
in accordance with this viewpoint
,

The Pos i ti on (Co ng u ra ti o n) i s D ete rmi ned by a Fi ni te N u mber

f Coordi na tes
I n ordinary mechanics this is actually the case i n every system
of a nite number of material points o r rigid b odies among whose
coordinates there exi st arbitrary xed equations of condition
I f we call the i ndependent coordinates go l go g o
then the
ext ernal work is :
o

5E ,

1 1 590 1

( 3

(5 8 )

wherein (13 1 CP2

are the e xternal force components which
correspond to the individual coordinates and E denotes the
energy of the system Then the principle of least action is
expressed by
,

dt

6H

6H

a
+
m
590 1
(9 90 1

= 0

From this follow the equations of motion :

d

6H

6H

a;

6 951

(990 1

(59 )

T hrough multiplication
and so on for all the indices 1 2 o
o
addition and integra
o
g
of the i ndividual equations by g l og
tion with respect t o time there res u lts the equation of conserva
tion of energy whereby the energy E is given b y the e x pression :
,

E =

I n ordinary mechanics H

or!

ol

a$0 1
.

if

(60 )

denote the kinetic and

G ENE R AL DYNAM I CS
U

P R I NC I P LE O F LEAST ACT I ON

1 01

the potential energy S ince L is a homogeneous function of

the second degree with respect to the go s it follows from (60 )
that :
.

E = 2L
Bu t

this expression holds by no means i n general

W e pass now to the consideration of the quasi -stationary
motion of a system of linear conductors carrying simple closed
galvanic currents Th e state of the system is given by the
position and the velocities of the conductors and by the cur
rent densities i n each of the same Th e coordinates referring
to the position of the rst conductor may be represented by
"
corresponding designations holding for the
col
go l
go l
remaining conductors W e inquire now as to the increase of
energy or the external work A which corresponds to a virtual
displacement of all coordinates E nergy may be conveyed to
the system through mechanical actions and through electro
magnetic induction as well The former corresponds to mechan
ical work the latter to electromotive work The former will
be of the familiar form :
.

l i 5se i

( 9

'

5s0 1

(19

590 2

I f we denote by E 1 E 2
t h e electromotive forces which
are induced i n the individual c onductors throug h ext ernal
agencies (e g moving magnets which d o not belong to the
system ) then the electromotive work done from outside upon
the currents i n the conductors of the system is :
,

E 1 56 1

E 256 2

if 56 1 56 2
denote the quantities of electricity which pass
through cross sections of the conductors due to i nnitely small
Virtual currents Th e nite current densities will then be denoted
T h e electrical state of the rst conductor is
by 61 g
thus determined i n general by the current density l the
mechanical state (position and velocity ) by the coordinates
,

S E V ENTH LECTURE

1 02

"

and the corresponding velocities e1 gol gol

are so -called cyclical coordinates
Th e coordinates c l 6 2
since the state does not depend upon their momentary values
but only upon their differential quotients with respect to time
j ust as for example the state of a body rotatable about an axis
of symmetry depends only upon the angular velocity and not
upon the angle of rotation Th e scheme of notation adopted
permits of the direct application of the above formularization
of the principle of least action to the case here considered
H where H the mechanical potential depends
Ha,
T hus H
onl y upon the go s and go s while the electrokinetic potential H
takes the following form :
ga l , go l

'

go l

e,

1 1 2 61 62
L1 3 l 3
E-Ll l l
%L
L22
the coe fcients of self
Th e quantities L1 1 L I 2 L1 3
induction and mutual i nduction depend however i n a denite
manner upon the coordinates of position ga l go l
go 2

2
22 2

S0 2

P2

I n accordance with
conductor :
pl

we h ave for the motion of the rst

M

d
(i t

6H,

a$0 1

6 90 1

with corresponding equations for gol

current i n it :
d

E1

laws for the mechanical

condensed into the statement
force upon the rst conductor
c h a ni c a l force
6 80 1

1 6 L1 1
2 am

61

go l

6 90 1

6H ,
,

0,

o o o and for the electric

0

di

Th e

6H

'

6H

(ponderomotive ) actions ma y be
that i n addition to the ordinary
I>1 there i s a me
expressed by <

<
9n
6 $0 1

1 2

6 L1 3

"
i

"

6 90 1

which is composed of an action of the current upon itself (rst

term ) and of the actions of the remaining currents upon it
(following terms )
.

ENE R AL DYNAM I C S

P R I NC I PLE

OF

LEA S T ACT I O N

laws of electrical action on the other hand are expressed

by the statement that to the external electromotive force E ;
I n the rst conductor t h e re is added the electromotive force
Th e

d II

dt

agl

Ln l
(
dt

L1 2 9

L1 3 3

which likewise i s composed of an action of the current upon itself

(self induction ) and of the inducing actions of the remaining
currents and that these two forces compensate each other
Th e galvanic conductance or the galvanic resistance is not
contained i n these equations because the correspon d ing energy
J oule heat is produced i n an irreversible manner and irreversible
processes are not represented by the principle of least action
One can formally include this action likewise any other irre
v e rsible action i n accordance with the procedure of Helmholz
b y introducing it as an external force i n the present case as
t h e electromotive force due to the resistance 10 which operates
to cause a diminution in the energy of the system For an
i nnitely small element of time the amount of this energy change
,

13 :

(10 1 6

2
w2 2

2
s 3

dt

(wl e l d el

10 2 6

since the external work E 1 de 1

E gd g
now
i ncludes the J oule heat the external force components E 1 E 2 o
i n the electromotive equations must be increased by the addi
wz z
wl l
t i o na l terms
Th e application O f t h e principle of least action to thermo
dynamic processes is Of special interest because the importance
of the question rel ating to th e xing of the generalized coor
d ina t e s which determine the state of the system here becomes
prominent
From the standpoint of pure thermodynamics
the variables which determine the state of a body can certainly
be quite arbitrarily chosen e g i n the case of a gas of invariable
constitution any two of the following quantities may be chosen
C onsequently

SE V ENTH LECTURE

1 04

as indep endent variables and all others expressed t h rough them :

volume V temperature T pressure P energy E entropy S I n
the present case the matter is quite di ff erent I f we inqu i re I n
order to apply the principle of least action with regard to the
energy change or the total work A which will be done upon the
gas from without in an innitely small Virtual displacement it
may be written in the form :
,

T58

is the heat added from without

p 5 V the mechanical work
furnished from without I n order to bring this into agreement
with the general formula for external work
,

1 1 590 1

( 3

'

i (P25S0 2

it becomes necessary now to choose V and S as the generalized

coordinates of state and therefore to identify with them the
previously employed quantities go l and gp g Then
p and T
are the generalized force components i n and CD2 N ow since in
thermodynamics every reversible change of state proceeds with
innite sl owness the velocity components and S and in general
all differential coefcients with respect to time are to be placed
equal to zero and the principle of least action (5 9 ) reduces to :
,

OH

0,

and therefore in our case :

,

6V

= 0

T+

and

Further in accordance with

,

E
N ow

these equations are actually valid since they only present

other forms of the relation
,

dS =

dE

p dV

G ENE R AL D YNAM I CS

P R I NC IP LE O F LEAST ACT I ON

1 05

view here presented is fundamentally that which is given

in the energetics of M ach Ostwald Helm and Wi e d e b u rg T h e

generalized c oordinates V and S are i n this theory the capac

1
ity factors
intensity factors
S o long as
p and T the
one limits himself to a n irreversible process nothing stands in
the way of carrying out this method completely nor of a gener
a li z a t i o n to include chemical processes
I n opposition t o it there is an essentially different method of re
garding thermodynamic processes which i n its complete general
ity was rst introduced i nto physics by Helmholtz I n accordance
with this method one generalized coordinate i s V and the other

is not S but a certain cyclical coordinate we shall denote it

as i n the previous example by e which does not appear itself

in the expression for the kinetic potential H and only appears
through its di ff erential coefcient ; and this di ff erential coef
c i e nt is the temperature T
Accordingly H is dependent only
upon V and T T h e equation for the total external work in
accordance with
is :
T he

p 5V

+ E 56

and agreement with thermodynamics is obviously found if we

set :
T5S ,

E55

Th e

Ed e

and also :

TdS ,

E dt

dS

equations (59 ) for the principle of least action become :

= 0

and

dt

= 0,

6T

or
E dt

dS

eakin g p f t h e e n erg y d iff erent ial i nto t w o fa tor b y t h

t
f e n erg e t i
i b y no m e an a o i a t e d w i t h a pe i al p ro pert y f
p
en erg y b t i i m pl an e pre ion f t h e el e m ent ary law t hat t h d iff erent i al
f a f n t i on F ( ) i e q al to t h e p o d t f t h e d i ff er e nt i al d b y t h e d eri va
t ive F
1

Th e b r

o ne n s o

cs

s s

ss

or

ss

uc

as

e ex

SE V ENTH LECTU R E

1 06

or by integration :

to an additive constant which we may set equal to

energy there results i n accordance with
,

For the

and consequentl y:
H

TS )
(E

H is therefore equal t o the negative of the function which

Helmhol z has called the free energy of the system and the
above equations are known from thermodynamics
Furthermore the method of Helmholz permits of b eing carried
throug h consistently and s o l ong as one limits himself t o the
consideration of reversible processes it is i n general quite i m
possible t o decide i n favor of the one method or the other How
ever the method o f Helmhol z possesses a distinct advantage
over the other which I desire t o emphasize here I t lends itself
b etter t o the furtherance of our endeavor toward the unication
of the system of physics I n accordance with the purely energetic
method the independent variables V and S h ave absolutel y
nothing t o d o with each other ; heat i s a form of energy which i s
distinguished i n nature from mechanical energy and which i n
no wa y can be referred back t o it I n accordance with Helmhol z
heat energy is reduced t o motion and this certainly indicates an
advance which is t o b e placed perhaps upon exactly the same
footing as the advance which i s i nvolved i n the consideration of
light waves as electromagnetic waves
T o be sure the View of Helmholz is not broad enough to include
irreversible processes ; wit h regard t o this as we have earlier
stated in detail the introduction of the calculus of probability
is necessary i n order t o throw light on the question At the
same time this is also the real reason that the exponents of
,

ENE R A L DYNAM I C S

P R I NC I PLE

OF

LEA S T ACT I O N

energetics will have nothing t o d o with the strict observance

of irreversible processes and they either declare them as doubtful
or ignore them completely I n reality the facts of the case are
quite the reverse ; irreversible processes are the only processes
occurring i n nature R eversible processes form only an ideal
abstraction which is very valuable for the theory but whic h is
never completely realized in nature
,

'

II

The Genera li zed Co ordi na tes

t
r
a
t
e
F
o
m
S
f

Ma nifold

Co nti nuou s

Th e

laws O f innitely small motions of perfectly elastic bodies

furnish us with the simplest example Th e coordinates of state
are then the displacement components
of a material
by
point from its position of equilibrium
y z ) considered as a
function of the coordinates x y z Th e external work is given
by a surface integral :
.

da o

mn
,

nan
,

5b z )

surface element ; 22 inner normal ) Th e kinetic potential

is again given by the difference of the kinetic energy L and the
potential energy U :
H
L
U
Th e kinetic energ y is :
(do ,

(be

by

be) .

wherein d r denotes a volume element k the volume densit y

Th e potential energy U i s likewise a space i ntegral of a hom o
g e ne o u s quadratic function f whic h species the potential energy
of a vol ume element T his depends as is seen from purely
geometrical considerations onl y upon the 6 strain coefcients
.

an,
6 2:
an,

an.

6 2:

63
/

an.
yz

zy

dx

an,

an.

6y

dz

an,
dz

an,
2

6 3/

an,
6 2:

S E V ENTH LECTURE

1 08

I n general therefore the function f contains 2 1 independent

constants which characteriz e the whole elastic behavior of the
substance For isotropic substances these reduce on grounds
of symmetry to 2 S ubstituting these values i n the expression
for the principle of least actio n (5 7 ) we O btain :
,

dr

x.

~
+

axy

I f we put for brevity

6f

af

Y2

ag z

Yy

6 y,

dz,

6f

6f

1:

azz

6f
2;

Y;
3

ax?!

it turns out as the result of purely mathematical operations i n

which the variations 5b
and likewise th e variations
are reduced throug h suitable partial integration with
respect to the variations 5b 5b, o
that the conditions within
the bod y are expressed by :
,

, ,

, ,

6 X,

6 X,

6 X:

By

6 2:

0,

and at the surface by :

,

X cos

X, cos

X cos

vy

vz ,

as i s known from the theory of elasticity Th e mechanical sig

o
i
n
X
Y
as surface forces follows
n c a c e of the quantities
,
from the surface conditions
For the last application of the principle of least action we will
take a special case of electrodynamics namely electrodynamic
processes i n a homogeneous isotropic non-conductor at rest e g
a vacuum Th e treatment is analogous to that carried out in the
foregoing example Th e onl y di ff erence lies i n the fact that in
.

, ,

ENE R A L DYNAM I C S

P R I NC I PLE

OF

LEA S T ACT I O N

electrodynamics the dependence of the potential energy U upon

the generalized coordinate b i s somewhat di fferent than i n elastic
phenomena
W e therefore again put for the external work :
.

mn

da g

mm)

R an,

(6 1 )

and for the kinetic potential :

U

wherein again :
I:
T

On t h e other

D +
(

Dy

Dz

hand we write here :

,

dr

(curl D)

T hrough

these assumptions the dynamical equations including

the b oundary conditions are now completely determined The
principle of least action (5 7 ) furnishes :
.

f ff
dt

wab

dr k

d r h(c u rl, , na curl , n

0

From this follow i n quite an analogous way to that employed

above i n the theory of elasticity rst for the interior of the
non-conductor :
a curl b
6 curl y I)
,

k6,

By

6 2:

or more briey
k6

curl curl

(62)

b,

and secondly for the surface :

,

Iz(c u rl z I)

cos

vy

curl y

cos

T hese

vz

(63)

equations are identical with the known electrodynam i cal

equations if we identify L with the electric and U with the
,

S E V ENTH LE CTURE

1 10

magnetic energy (or conversely )

L

dr

I f we put

and

dr

[1

5:

E and 9 the eld strengths 6 the dielectric constant p the

(C
permeability) and compare these values with the above expres
sions for L and U we may write :
.

f3

47

I t follows then by elimination of

,

I) ,

(64 )

that :
curl C53
,

and further by substitution of f) and curl b i n equation (62) found

above for the interior of the non-conductor t h at :
,

(S

e e

curi s

C omparison

pressed

in

wit h the known electrodynamical equations ex

Gaussian units :
a

c c u rl

(c velocity of light i n vacuum ) results in a complete agreement

,

if we put :
and
C

From either of these two equations it follows that :

h

It

the square of

he

velocity of propagation

W e obtain from (6 1 ) for the energy entering th e system from

without :
di

d0 (X x
'

v )
z

ENE R A L DYNAM I C S

P R I NC I PLE

LEA S T A CT I O N

OF

or taking account of the surface equ a tion

,

dt

d orh { (c u rlz t)

cos

curl y

vy

t)

Z
)D

cos

an expression which upon s u bstit ution of the values of 6 and curl

turns out to be identical with the Poynting energy
b from
current
W e have thus by an application of the principle of least action
with a suitably chosen expression for the kinetic potential H
arrived at the known M axwelli a n el d equations
Are then the electromagnetic processes thus referred back to
mechanical processes ? By no means ; for the vector 6 employed
here i s certainly not a mechanical quantity I t is moreover n o t
possible i n general to interpret b as a mechanical quantity for
instance I) as a displacement 6 as a velocity curl t) as a rotation
T hus e g i n an electrostatic eld i) is constant
T herefore
6 increases with the time beyond all limits and curl I) can
1
no longer signify a rotation
While from these considerations
the possibility of a mechanical explanation of electrical phenom
ena is not proven it does appear on the other hand to b e u m
doubtedly true that the signicance of the principle of least
action may be essentially extended beyond ordinary mechanics
and that this pri nciple can therefore also be utilized as the
foundation for general dynamics since it governs all known re
v e rsi b le processes
,

eg a d to t h e i m p o ib i l i t y f i nt e pre t i ng el e trod yn am i pro e e

i n t erm f t h e mot i on f a ont i n o m ed i m f p art i larl y H W i tt e :
Ub er d n g g wa t ig S t an d d Frag e n a h e i n er m e han i h e n E kla
g
el ektri h en Er h ein ng en B erl i n 1 9 06 (E E b eri ng )
d
1

Wi t h

ss

s O

s o

er

sc

en

sc

en

us

er

cu

sc

ss s

ru n

E I GHT H LE C T UR E

GE N E RA L

D Y N AM I CS

PRI NC I P LE

R ELAT IVI TY

OF

I n the lecture of yesterday we saw by means of examples

that all continuous reversible processes of nature may be re p re
sented as consequences of the principle of least action a n d
that the whole course of such a process is uniquely determined
as soon as we know besides the actions which are exerted upon
the system from without the kinetic potential H as a function
O f the generalized coordinates and their differential coefcients
with respect to time Th e determination of this function
remains then as a special problem and we recognize here a
rich eld for further theories and hypotheses I t i s my purpose
to discuss with you today an hypothesis which represents a mag
ni c e nt attempt t o establish quite generally the dependenc y of
the kinetic pot ential H upon the vel ocities and which i s commonl y
d esignated as the principle of relativity
Th e gist of this prin
c ip le is : it i s i n n o wise possible t o detect the
motion of a
bod y relative t o empty space ; i n fact there is absolutely
no physical sense i n speaking O f such a motion I f therefore
two observers move with uniform but di ff erent velocities then
each of the two with exactly the same right ma y assert that with
r espect t o empt y space h e i s at rest and there are no physical
methods of measurement enabling us t o decide i n favor of the one
or the other The principle of relativity i n its generalized form
is a very recent development Th e preparatory steps were taken
by H A L orentz it was rst generally formulated by A E instein
and was developed into a nished mathematical system by
H M inkowski However trace s of it extend quite far back
into the past and therefore it seems desirable rst to say some
thing concerning the history o f its development
,

1 12

ENE R AL DYNAM I C S

P R I NC I PLE

OF

R ELAT I V I TY

Th e

principle of relativity has been recognized i n mechanics

since the time of Galilee and N ewton I t is contained i n the
form of the simple equations of motion of a material point since
these contain only the acceleration and not the vel ocity of
the point I f therefore we refer the motion of the point
rst to the coordinates a y z and again to the coordinates
x
y z of a second system whose axes are directed parallel
to the rst and which moves with the velocity V i n the d ire c
tion of the p ositive x -axis :
.

Vt,

y,

(65)

z,

and the form of the equations of motion is not changed i n the

slightest N othing short of the assumption of the general val
id it y of the relativity principle i n mechanics can u st ify the i nc lu
sion by physics of the C opernican cosmical system si nce through
i t the i ndepe n dence of all processes upon t he earth of the p ro gre s
sive motion of the earth is secured
I f one were obliged to take
account of this motion I should have e g to admit that the piece
of chalk i n my hand possesses an enormous kinetic energy corre
sp o nd i ng to a velocity of somethi ng like 30 kilometers per second
I t was without doubt his conviction of the absolute valid
ity of the principle of relativity which guided Heinri c h Hert z
in the establishment of his fundamental equations for the elec
Th e electrodynamics of Hert z
t ro d yna m i c s of moving bodies
is i n fact wholly built upon the principle of relativity I t recog
I t speaks
n iz e s no absolute motion with regard to empty space
only of motions of material b odies relative t o one another I n
accordance with the theory of Hertz all electrody namic pro
cesses occur i n material bodies ; if these move then the electro
dynamic processes occurring therein move with them To speak
of an independent state of motion of a medium outside of material
bodies such as the ether has j ust as little sense i n the theory of
Hertz as i n the modern theory of relativity
B u t t h e theory of Hertz has led to various contradictions with
experience I will refer here to the most important of these
.

E I GHTH LECTU R E

1 14

Fizeau brought (1 8 5 1 ) int o parallelism a bundle of rays origi

nating i n a light source L by means of a l ens and then broug h t it
to a focus by means of a second lens upon a screen S (Fig
.

FI G 2
.

I n the path of the parallel light rays between the two lenses h e
placed a tube system of such s ort that a transparent liquid could
be passed through it and i n such manner that i n one half (the
upper ) the light rays would pass i n t h e direction of ow of the
liquid while i n the other half (the l ower ) the rays would pass in
the opposite direction
I f now a l iquid or a gas o w through the tube system with the
velocity V then i n accordance with th e theory of Hertz since
light must b e a process i n the substance the light waves m u st
be transported with the velocity of the liquid Th e v e lo c
ity of light relative to L and S i s therefore i n the upper part
V and th e l ower part qo
V if qo denote the velocity
qo
of light relative t o the liquid Th e difference of these two
velocities 2 V shoul d be observable at S through corresponding
interference of the l ower and the upper light rays and quite i nde
pendently of the nature of the owing substance E xperiment
did not conrm this conclusion M oreover it showed i n gases
generally no tr ace of the expect e d action ; i e light is propagated
in a owing gas in the same manner as i n a gas at rest On the
other hand i n the case of liquids an effect was certainly indicated
,

GENE R AL DYNAM I CS

P R I NC I P LE O F RELAT I V I TY

115

but notably smaller i n amount than that demanded by the theory

of Hertz I nstead of the expected velocity diff erence 2 V the
2
di ff erence 2 V (1
l /n ) only was observed where n is the re
2
fra c t i v e index of the liquid
Th e factor (1
1 / n ) is called
the Fresnel coefcient T here is contained (for n
1 ) in this
expression the result obtained i n the case of gases
I t follows from the experiment of Fizeau that as regards
electrodynamic processes i n a gas the motion of the gas is
practically immaterial I f therefore one holds that electro
dynamic processes require for their propagation a substantial
carrier a special medium then it must be concluded that this
medium the ether remains at rest when the gas moves i n an ar
bit ra ry manner This interpretation forms the basis of the elec
t ro d yna m i c s of L orentz i nvolving an absolutely quiescent ether
I n accordance with this theory electrodynamic phenomena have
only i ndirectly to d o with the motion of matter Primarily all
electrodynamical actions are propagated in ether at rest M atter
inuences the propagation only i n a secondary way s o far as it
is the cause of exciting i n greater or less degree resonant vibrations
in its smallest parts by means of the electrodynami c waves
passing through it N ow since the refractive properties of sub
stances are also inuenced through the resonant vibrations of its
smallest particles there results from this theory a denite con
ne c t i o n between the refractive index and the coefcient of Fresnel
and this connecti o n is as calculation shows exactly that de
S o far therefore the theory of
m a nd e d by measurements
Lorent z is conrmed through experience and the principle of
r e lativity i s divested of its general signicance
Th e principle of relativity was immediately confronted by
a new dif culty Th e theory of a quiescent ether admits the
idea of an absolute velocity of a body namely the velocity
relative t o the ether Therefore in accordance with this theory
of two O bservers A and B who are in empty space and who
move relatively to each other with the uniform velocity V it woul d
be at best possible for only one rightly to assert that he is at
.

E I GHTH LE CTUR E

1 16

rest relative to the ether I f we assume e g that at the moment

at which the two observers meet an i nstantaneous O ptical signal
a ash is made by each then an i nnitel y thin spherical wave
spreads out from the place of its origin i n all directions through
empty space I f therefore the observer A remain at the center
of the sphere the observer B will not remain at the center and
as j udged by the observer B the light in his own direction of
motion must travel (with the velocity 0
V ) more slowly than
i n the O pposite direction (with the velocity 0
V ) or than i n a
perpendicular direction (with the velocity
(cf Fig
,

ac

Fi g 3
.

Under

suitable conditions the observer B should be able to

detect and measure this sort of effect
T his elementary consideration led t o the celeb rated attempt
of M iche lson t o measure the motion of the earth relative to the
ether A parallel beam of rays proceeding from L (Fig 4 )
falls upon a transparent plane parallel plate P inclined at
by which it is i n part transmitted and i n part reected Th e
transmitted and reected beams are brought int o interference
by reection from suitable metallic mirrors S I and S2 which are
removed by the same distance I from P I f now the eart h with
the whole apparatus moves in the direction P S I with the velocity
V then the time which the light needs in order to go from P to
S I and back is :
.

ENE R A L DYNAM I C S
l

P R I NC I PLE

l
V

On

OF

R E LAT I V I TY

the other hand the time which the light needs i n order to pass
from P t O S 2 and back to P is :
,

'

2l

2P

I f now the whol e apparatus be turned through a right angle a

noticeable displacement of the interference bands should result
,

Sn

Fi g 4
.

since the time for the passage over the path P S 2 is now longer
N o trace was observed of the marked eff ect to be exp ected
N o w how will it be possible to bring into line this res ul t
e stablished by repeated tests with all the facilities of modern
experimental art ? E C ohn h as attempted to nd the ne c e s
sary compensation in a certain inuence of the air in whi ch
the rays are propagated Bu t for anyone who bears in mind the
great results of the atomic theory of dispersion and who does
not renounce the simple explanation which this theory gives for
the dependence of the refractive index upon the color without
introducing something else in its place the idea that a mo v ing
.

E I GHTH LE CTURE

1 18

absolutely transparent medium whose refractive inde x is a b s o

lu t e ly
1 shall yet have a notable inuence upon the velocity
of propagation of light as the theory of C ohn demands is not
possible of assumption For this theory distinguishes essentially
a transparent medium whose refractive index is
1 from a
perfect vacuum For the former the velocity of propagation of
light i n the direction of the velocity V of the medium with relation
to an O bserver at rest is
,

e
for a vacuum on the other hand q
I n the former medium
C ohn s theory of the M ichelson experiment predicts no effect
but on the other hand the M ichelson experiment shoul d give
a positive effect i n a vacuum
I n O pposition t o E C ohn H A Lorent z and Fit z Ge ra ld
ascribe the necessary compensation t o a contraction of the whole
optical apparatus i n th e direction of the earth s motion of th e
2
2
order of magnitude V / c
This assumption allows better of the
introduction again of the principle of relativity but it can rst
completely satisfy this principle when it appears not as a n e c e s
sar y hypothesis made to t the present special case but as a
consequence of a much more general postulate W e have to
thank A E instein for the framing of this postulate and H Mi n
ko wski for its further mathematical development
Ab ove all the general principle of relativity demands the
renunciation of the assumption which led H A Lorentz to the
framing of his theory of a quiescent ether ; the assumption
of a substantial carrier of electromagnetic waves For when
such a carrier is present one must assume a denite velocity of a
ponderable body as denable with respect to it and this is exactly
that which is excluded by the relativity principle Thus the
ether drops out of the theory and with it the possibility of
mechanical explanation of electrodynamic processes i e of re
ferring them to motions Th e latter di fculty however does
,

G ENERA L DYNAM I CS

P R I NC I P LE O F RELAT I V I TY

1 19

not signify here so much since it was alre a dy kno w n before

that no mechanical the ory founded upo n the conti nuous motions
of the ether permits of being completely carried through (cf p
I n place of the s o called free ether there i s now substituted
1
the absolute vacuum i n which electromagnetic energy i s inde
pendently propagated like ponderable atoms I belie v e it follows
as a consequence that no physical properties can be consistently
ascribed to the absolute vacuum The dielectric constant and the
magnetic permeability of a vacuum have no absolute meaning
onl y relative I f an electrodynamic process were to occur i n a
ponderable medium as i n a vacuum then i t woul d have absolutely
no sense to distinguish between eld strength and induction
I n fact one can ascribe to the vacuum any arbitrary value of the
dielectric constant as is indicated by the various systems of
units B u t h o w i s it no w with regard t o the velocity of p ro p a
?
T
of
light
his
also
i
s
not
to
be
regarded
as
a
property
of
i
a
t
o
n
g
the vacuum but as a property of electromagnetic energy which
is present i n the vacuum Where there is no energy there can
exist no velocity of propagation
With the complete elimination of the ether the opportunity i s
now present for the framing of the principle of relativity Ob
we must as a simple consideration shows introduce
V i o u sly
something radically new I n order that the moving observer
B mentioned above (Fig 3 p 1 1 6) shall not see the light
signal given by him travelling more sl owly i n his own direction
of motion (with the velocity 0
V ) than in the opposite direction
(with the velocity 0 + V ) it i s necessary that he sh all not identify
the instant of time at which the light has covered the distance
V i n the direction of his own motion with the i nstant of time at
0
which the light has covered the distance 0
V i n the opposite
direction but that he regard the latter instant of time as later
I n other words : the observer B measures time differently from
the observer A T his is a priori quite permissible ; for the
relativity principle only demands that neither of the two observers
shall come into contradiction with himself However the
,

1 20

E I G I IT I I

LECTURE

possibility is l e ft open that the specications of time of both

observers may be mutually contr a dictory
I t ne e d scarcely be emphasized that this n e w conception of the
idea of time makes the most serious demands upon the capacity
of abstraction and the projective power of the physicist I t
surpasses i n boldness everything previ ously suggested i n sp e c u
lative natural phenomena and even i n the philosophical theories
of knowledge : non-euclidean geometry is child s pla y i n com
parison And moreover the principle of relativity unlike non
euclidean ge ome try which onl y comes seriously into consider
ation i n pure mathematics undoubtedly possesses a real physical
signicance Th e revolution i ntroduced by this principle i nto
the physical conceptions of the world i s only to be compared in
extent and depth with that brought about by the i ntroduction
of the C opernican system of the universe
Since it is difcult on account of our habitual notions con
cerning the idea of abs o lute time t o protect ourselves without
S pecial carefull y considered rules against l ogical mistakes in the
necessary processes of thought we shall adopt the mathematical
method of treatment Le t us consider then a n ele c trodynamic
p rocess i n a pure vacuum ; rst from the standpoint of an O b
server A ; s e c o nd ly from the standpoint of an observer B who
moves relatively to observer A with a velocity V i n the direction
of the :r-axis T hen i f A empl oy the system of reference a y z t
and B the system of reference x y z t our rst problem is to
nd the relations among the primed and the unprimed quantities
Above all it is to be noticed that since both systems of reference
the primed and the unprimed are to be like directed the equa
tions of transformation between corresponding quantities i n the
two systems must be s o established that it is possible through
a transformation of exactly the same ki nd t o pass from the rst
system to the second and conversely from the second back to
t h e rst system I t foll ows immediately from this that the velocity
of light 0 i n a vacuum for the observer B is exactly the same
as for the O bserver A T hus if c and c are di fferent 0
c
.

ENE R AL DYNAM I C S

P R I NC I PLE

R ELAT I V I TY

OF

say it would follow that : if one passes from one observer A to

another observer B who moves with respect to A with uniform
velocity then h e woul d nd the velocity of propagation of light
for B greater than for A T his conclusion must likewise hold
quite i n general i ndependently of the directi on i n which B moves
with respect to A because all directions i n space are equivalent
for the observer A On the same grounds i n passing from B to
A 0 must be greater than c for all directions i n space for the
observer B are now equivalent S ince the two inequalities con
Of course this impor
t ra di c t therefore 0 must be equal to 0
tant result may b e generalized immediately so that the totality
of the quantities I ndependent of the motion such as the
v elocit y of light in a vacuum t he constant of gravitation
between two bodies at rest every isolated electric charge and
the entrop y of any physical system possess the same values for
both observers O n the other hand this law d oes not hold for
quantities such as energy volume temperature etc For these
quantities depend also upon the velocity and a body which is
at rest for A i s for B a moving body
W e inquire now with regard to the form of the equations
of transformation between the unprimed and the primed coor
For this purpose let us consider returning to the
d i na t e s
previous example the propagation as it appears to the two
observers A and B of an instantaneous signal creating an i n
nit e ly thin light wave which at the instant at which the o b s e rv
ers meet begins to spread out from the common origin of
coordinates For the O bserver A the wave travels out as a
spherical wave :
,

2 2

(66)

For the second observer B the same wave also travels as a

spherical wave with the same vel ocity :
:r

0;

(67 )

for the rst O bserver has no advantage over the second obser v e r
9

E I G HTH LECTURE

1 22

c a n ex a ctly w ith t he same right as A assert that he is at rest

a t the c e nter of the sp h eric a l wa v e a nd for B after u nit time the
B

wave a ppea rs a s i n Fig 5 whil e its a ppeara nce for the observer
A a fter u nit time i s represented by Fig 3 (p
T he equ a t ions of transform a tion must t herefore fulll the
conditi on th a t t h e t w o l a st equ a tions which represent the s a me
ph y sic a l process a re comp atibl e wit h e a ch other ; a nd further
more : t he p a ss a ge from t h e unprimed t o t he primed qu a ntities
mu s t i n no wise b e distinguished from the reverse p a ss a ge from
th e prim e d t o the unprimed qu a ntities
I n order to satisfy
these conditions we genera lize the equ a tions of tr a nsform a ti on
(65 set up a t t h e beginning of this lecture for the old mechanic a l
rinciple
of
r
i n the following manner :
e l a tivit y
p
,

(r

Vt

X31

as ,

'

V!

Here V denotes a s formerl y the vel ocit y of the obser v er B rel ative
t o A a nd the const a nts K A ) 1 V p a re yet t o be det ermined \Ve
must ha v e :
.

:1

I t is no w

T)

Xy

31

'

"
S

'

1
t o s e e th a t a nd N must both
For if e g
T h e c i rc u m st n e t ha t t h e s ig n a l i s a fi n i t e on e h o weve r s m all t h e t i m e
i g n i fi a n e on l a s r ga ds t h t h i kn e s o f t h e s p h er i c al lay er
m
b h
t h e on l u si on h ere n d e r on i d e rat i on
an d n t f
e a sv

ay

e,

as

or

( I ICN IJ It A I.

YNAM I C S

"R

O I

LAT I V I TY

g re at e r tha n 1 th e n X m ust a ls o b e g re a t e r th a n 1 fo r t he
t wo t ra n s f o r m a t i o ns a re e q ui v a l e n t w ith r e g a rd t o t he y
/ a xis
In p a rticul a r i t is im p ossi bl e th a t A a nd N d e p e nd u p o n t he
d ir e ctio n of m otio n o f t he oth e r o bs c c r
Iu t no w si nc e i n
a cco rda nc e wit h w ha t p r e e d e s A
l / A e a c h o f t he two
in e qualiti e s c o ntr a di c t a nd th e r e fo r e
I ; lik e w is e
l
T he c o nd iti o n fo r i d e nti t y o f t he t w o sph e ri c a l
[1
n
wa ve s t h e n d e m a nd s th a t t he e x p r e ssi o n
A be

b e com e t hro u g h t he tr a ns fo r m a ti o n o f co o rd i na t e s i d e nti c a l w ith

t he expr e ssio n
,

""
7

and from t his the e quati o ns o f tr a nsfo r m a ti o n foll o w with o ut

a m big u ity :
:r

Vt

=
y
y,
I

t =
I

2,

t s
(

(08 )

wh e r e in
K

J o n ve rs e ly :
y

t =

T h e se

(6 9 )

e quatio ns p e r mi t q u it e i n g e n e r a l o f t h p a ss a g e from t he
s yst e m of r e f e rence of o ne ob s e r ve r t o that o f the oth e r (II A
Lor e ntz ) and t he p rinciple of r e lati vity as s e rts t hat a ll pro e ss e s
e

at u re occu r i n ac c ordance with t he s a m e laws a nd with t he

same co nsta nts fo r bot h ob se r v e rs (A l linst e in ) Ma t he m a t
ic a lly co ns id e r e d t he e q u atio ns of tr a nsformatio n cor respo nd to
i
z
a rotation i n th e four d im e n s ional sy st e m of r e f e r e nc e
e t)
y
through the ima g i na ry a ngl e a rc t g
(l l M i nko wski )
Accor d i ngly t he pri nci p l e o f r e l a ti v ity s i m p ly t e a c h e s th a t th e r e
is i n t he fo ur d i m e ns i o na l syst e m o f s p a c e a nd ti m e no S p e i a l
c hara c t e risti c d irect ion a nd a n y d o u bts c m i c c rni ng t he g e n e r a l
in

E I GHTH LECTU R E

1 24

validi ty of the principle are of exactly the same kind as those

concerning the existence of the a nt ip o d i a n s upon the other side
of the earth
W e will rst make some applications of the principle of
relativity t o processes which we have already treated above
T hat the result of the M ichelson experiment i s i n agreement
wit h the principle of relativity i s immediately evident ; for in
accordance with the relativity principle the inuence of a
uniform motion of the eart h upon processes on the earth can
under no conditions b e detected
W e consider now the Fizeau experiment with the owing
liquid (see p
I f the velocity of propagation of light in
the liquid at rest be again go then i n accordance with the
relativity principle go i s also the velocit y of the propagation
of light in the owing liquid for an O bserver who moves with
the liquid i n case we disregard the dispersion of the liquid ;
for the color of the light i s different for the moving O bserver I f
we call this observer B and the velocit y of the liquid as above
V we may employ immediatel y the above formulae i n the cal
culation of the velocity of propagation of light i n the owing
liquid j udged by an observer A at the screen S W e have only
to put
.

dx

dt

a nd

(1 0

to seek the corresponding value of

dx
dt

For this O bviously gives the velocity sought

N o w it follows directl y from the equations of transformation
(69 ) that :
.

dx
dt

se
x

V
Vi )
-

7
0

G ENERA L DYNAM I CS

P R I NC IP LE O F RELAT I V I TY

1 25

and therefore through appropriate substitution the velocity

sough t in the upper tube after neglecting higher powers i n V /c
and V / qo is :
,

90

j;

V CIO

qO +

and the corresponding velocity i n the lower tube is :

1

90

Th e

di ff erence

Of

the two velocities is

2V

2V

which is the Fresnel coefcient in agreement with the measure

ments of F iz e a u
Th e signicance of the principle of relativity extends not only
to optical and other electrodynamic phenomena but also to
all processes of ordinary mechanics ; b u t the familiar expression
2
(%7n q ) for the kinetic energ y of a mass point moving with
the velocity q i s incompatible with this p ri nc ip l
B u t on the other hand since all mechanics as well as the
rest of physics i s governed by the principle of least action the
signicance of the relativity principle ex t ends at bottom only to
the particular form which it prescribes for the kinetic potential
H and this form though I will not stop to prove it is char
a c t e ri z e d by the simple law that the expression
,

dt

for every space element of a ph y sical system i s an invariant

H

dt

with respect to the passage from one

bserver A to the other

E I GHTH LECTUR E

1 26

is i n this passage an i nvariant

H c
Le t us now make some applications of this very general law
rst to the dynamics of a single mass point i n a vacuum whose
state is determined by its velocity q Le t us call the kine tic
potential of the mass point for q
0 H o and consider now the
point at an instant when its velocit y is q For an observer
B who moves with th e velocity q with respect to the observer
A q
0 at this instant and therefore H
H o B u t now
since i n general :
,

we have after substitution :

2

'

H0 =

Ho

W it h this value of H the Lagrangian equations of moti on (59 )

of the previous lecture are applicable
I n accordance with
the kinetic energy of the mass point
amounts t o :
,

aH
,
_
_

ax

9 1
.

ay

aH
ae

dq

H0

(1

and the momentum to :

G

is called the transverse mass m g and d C/dq the longitudinal

mass m ; of the point ; accordingly :

C /q

mt

(c

HO
2 3 /2

'

G ENERAL DYNAM I CS

For q

0,

P R I NC IP LE O F R ELAT I V I TY

1 27

we have

I t is apparent if one replaces in the above expressions the constant

Ho by the constant me that the momentum is :
,

m oq

and the transverse mass :

m,

mo
9
c

2
2

and the longitudinal mass :

mo

ml

3 2

and nall y that the kinetic energy is :

,

771 0 0

Emoq

'

familiar value of ordinary mechanics %moq appears here

therefore onl y as an approx imate value These equations have
been e xperimentall y tested and conrmed through the measure
ments of A H Bu c he re r and of E Hupka upon the magnetic
deection of electrons
A further e x ample of the invariance of H o dt will be taken from
electrodynamics Le t us consider in any given medium an y
electromagnetic eld For an y volume element V of the medium
the law holds that V dt is i nvariant in the passage from the one
to the other observer I t follows from this that H V i s i nvariant ;
2

The

E I GHTH LECTUR E

1 28

the kinetic potential of a unit volume or the s p ac e dens i ty

ki neti c p otenti a l

is invariant
Hence the following relation exists ;
.

5
$8

C
53)

Z
'

C
S D

wherein CE and 8? denote the eld strengths and i ) and 53 the

corresponding i nductions Obviously a corresponding law for
5
the space energy density (553)
$ 8 will not hold
A t hi rd example is selected from thermodynamics
I f we
take the velocity q of a moving body the volume V and the
temperature T as independent variables then as I have shown
we shall have for the pressure
in the previous lecture (p
p and the entropy S the following relations :
.

5H
aV

and

6H
6T

since V / Vc
q i s invariant and S likewise i nvari a n t
2
2
it foll ows from the invariance of H / \lc q
(see p
2
2
that p is invariant and also that T/ \lc
q is invariant and
hence that :
N ow

and

two observers A and B would estimate the pressure of a

body as the same but the temperature of the body as different
A special case of this example i s supplied when the body
considered furnishes a black b ody radiation Th e black body
radiati on i s the only physical system whose dynamics (for quasi
stationary processes ) is known with absolute accuracy T hat the
black body radiation possesses inertia was rst pointed out by
F H a se nOh rl For black b ody radiation at rest the energy
4
E0
a T V is given by the S tefan -B oltzmann law and the entropy
i
4

S0
d
E
T
T
T
and
the
pressure
and
a
V
a
3
o
0
(
)
(
)
/
p
/

f
therefore in accordanc e with the above relations the kinetic
The

G ENE R AL DYNAM I CS

P R I NC IP LE O F RELAT I V I TY

1 29

potential i s :
a

H0

T V

Le t

us imagine now a black body radiation moving with the

velocity q with respect to the observer A and introduce an
observer B who is at rest (q
0 ) with reference to the black body
radiation ; then :

wherein
I
Ho

2 T 4 VI
I

T aking

account of the above general relations between T and

T V and V this gives for the moving black body radiation the
kinetic potential :

TV

from which all the remaining thermodynamic quantities : the

pressure p the energy E t h e momentum C the longitudinal and
transverse masses m ; and m , of the moving black body radiation
are uniquel y determined
C olleagues ladies and gentlemen I have arrived at the con
I have endeavored to bring before
e lusi on of my lectures
you in bold outline those characteristic advances in the present
system of physics w h ich in my opinion are the most important
Another i n my place would perhaps have made another and better
choice and at another time it is quite likely that I myself
should have done so Th e principle of relativity holds not only
for processes in physics but also for the physicist himself i n
that a xed system of physics exists in reality only for a given
physicist and for a given time Bu t as i n the theory of rela
t i v i t y there exist invariants i n the system of physics : ideas and
,

E I GHTH LECTUR E

1 30

laws which retain their meaning for all i nvestigators and for
all times and t o discover these invariants is always the real
endeavor of physical research W e shall work further i n this
direction i n order to leave beh ind for our successors w h ere pos
sible lasting results For if while engaged i n body and mind
in patient and often modest individual endeavor one thought
strengthens and supports us it i s this that we in physics work
not for the day onl y and for immediate results but so to speak
for eternity
I thank you heartily for the encouragement w h ich you have
given me I thank you no less for the patience with which you
have followed my lectures to the end and I trust that it may be
possible for many among you to furn i sh in the direction indicated
much valuable serv ice to our beloved science
,