à2 Z àS

à P - -à T -

à2 Z àv
A Look Back at the Op2 - op

Ehrenfest Classification à2 Z
àTop
-
oS
- ar;
à
à

wo Z (T . p) das thermodynamische Poten

spezifische
ist. Im allg
mit allen
tienten stet
Tilman Sauer einer .. U m
p . T - Eben
zu besprech
liegen.
Jedenfall
von Z sel
Das heisst
ganzen Ue
T z.
Phase Transitions and Critical Phenomena PTCP16
Coventry, UK, 8 April 2016 denn ein Sprung von Z wuerde ja wegen -1.
Volumen und Entropie bedeuten .
 Question:
Why do we talk about phase transitions
st nd
of 1 or 2 order?
Are there genuine PT of third order or higher?

It is often said that the Kosterlitz-Thouless transition is a transition of infinite order.

Synonymously, people often speak about phase transitions of first or second kind, or more
descriptively of discontinuous and continuous transitions.

Answer: The reason is mainly historical. The terminology goes back to Ehrenfest’s
classification of 1933.

c Springer-Verlag 1998
Arch. Hist. Exact Sci. 53 (1998) 51–81. !

The Ehrenfest Classification of Phase Transitions:

Introduction and Evolution
GREGG JAEGER
Communicated by R.H. STUEWER

Abstract

The first classification of general types of transition between phases of matter,

T. Sauer: A Look Back at the Ehrenfest Classification, PTCP2016 2
 particular systems (see below) the theoretical and experimental questions remain
much the same for all critical points. I n particular a dominant characteristic is the
large increase of the microscopic fluctuations in the vicinity of a critical point which
herald the approaching transition. Fluctuations of density, energy, magnetization,
higher-order transitions?
etc., can reach effectively macroscopic magnitudes and, correspondingly, the
related second thermodynamic derivatives (specific heats, susceptibilities, etc., as
mentioned above) and the intensities for the scattering of waves off the system
become very large or even tend to infinity at certain wavelengths.
Consequently a problem of central interest in the study of critical phenomena,
both experimentally and theoretically, is the determination of the asymptotic laws
G. Jaeger
governing the (1998): “By to
approach thea1970’s, a radically
critical point. simplified binary classification
Some of these, notably the of phase
‘one-third’
powertranstions intovanishing
law for the “first-order”
of and
the “continuous” transtions was
density discontinuity p,,-increasingly adopted.”
p G between coexisting
liquid and gas as a function of T, - T , strikingly demonstrated in figure 1, have a
fairly long history; others, such as the logarithmic divergence of the specific heat
C;, of helium at the lambda point and the near-logarithmic divergence of C, for
M.E.Fisher
argon (1967):
at its critical point, are more recent discoveries. Theories competent to make
t T h e original classification of transitions, due to Ehrenfest, which essentially recognized
only discontinuities in thermodynamic derivatives, rather than divergencies, is inappropriate
in the light of present theoretical and experimental knowledge. I t seems best, therefore, to
discard terminology such as ‘second order’ or ‘third order’ which is often confusing or
uninformative.

T. Sauer: A Look Back at the Ehrenfest Classification, PTCP2016 3

 Nuclear Physics B 736 [FS] (2006) 319–328

Properties of higher-order phase transitions

W. Janke a , D.A. Johnston b , R. Kenna c,∗
a Institut für Theoretische Physik, Universität Leipzig, Augustusplatz 10/11, 04109 Leipzig, Germany
b Department of Mathematics, School of Mathematical and Computer Sciences, Heriot-Watt University, Riccarton,
Edinburgh EH14 4AS, Scotland, UK
c Applied Mathematics Research Centre, Coventry University, Coventry, CV1 5FB, England, UK

Received 15 October 2005; received in revised form 7 December 2005; accepted 14 December 2005
Available online 27 December 2005

Abstract

T. Sauer: A Look Back at the Ehrenfest Classification, PTCP2016 4

 1. Introduction

In its original format, the Ehrenfest classification scheme identifies the order of a phase
transition as that of the lowest derivative of the Helmholtz free energy which displays a discon-
tinuity there [1]. Typical transitions which fit to this scheme are first-order solid–liquid–vapour
transitions and second-order superconducting transitions. There are, however, many transitions
characterised by divergent rather than discontinuous behaviour. Examples include ferromag-
netic transitions in metals and the spontaneous symmetry breaking of the Higgs field in particle
physics, which display power-law or logarithmic divergent behavior as the transition is ap-
proached. The classification scheme has, in practice, been extended to encompass these scenarios
and the order of a transition is commonly given by the order of the lowest derivative in which
any type of non-analytic behaviour is manifest.

References

[1] P. Ehrenfest, Commum. Kamerlingh Onnes Lab. Leiden 20 (Suppl. 75B) (1933) 8.
[2] P. Kumar, D. Hall, R.G. Goodrich, Phys. Rev. Lett. 82 (1999) 4532.
[3] B.F. Woodfield, D.A. Wright, R.A. Fisher, N.E. Philips, H.Y. Tang, Phys. Rev. Lett. 83 (1999) 4622.
[4] P. Kumar, J. Low Temp. Phys. 106 (1997) 705.
[5] P. Kumar, A. Saxena, Philos. Mag. B 82 (2002) 1201;
P. Kumar, Phys. Rev. B 68 (2003) 064505.
[6] A.K. Farid, Y. Yu, A. Saxena, P. Kumar, Phys. Rev. B 71 (2005) 104509.
[7] T. Berlin, M. Kac, Phys. Rev. 86 (1952) 821.
[8] K. Kanaya, S. Kaya, Phys. Rev. D 51 (1995) 2404;
H.G. Ballesteros, L.A. Fernández, V. Martín-Mayor, A. Muñoz Sudupe, Phys. Lett. B 378 (1996) 207;
T. Sauer: A Look Back at the Ehrenfest Classification, PTCP2016 5
 [1] P. Ehrenfest, Commum. Kamerlingh Onnes Lab. Leiden 20 (Suppl. 75B) (1933) 8.
[2] P. Kumar, D. Hall, R.G. Goodrich, Phys. Rev. Lett. 82 (1999) 4532.
[3] B.F. Woodfield, D.A. Wright, R.A. Fisher, N.E. Philips, H.Y. Tang, Phys. Rev. Lett. 83
Ehrenfest and Heike Kamerlingh Onnes:

co-authored paper?
P. Ehrenfest, H. Kamerlingh Onnes, Simplified deduction of the formula
from the theory of combinations which Planck uses as the basis of his
radiation-theory. Proceedings Koninklijke Akademie van Wetenschappen
17: 870-873 (1914)
P. Ehrenfest, H. Kamerlingh Onnes, Vereinfachte Ableitung der
kombinatorischen Formel, welche der Planckschen Strahlungstheorie
zugrunde liegt. Annalen der Physik 351: 1021–1024 (1915)
P. Ehrenfest, H. Kamerlingh Onnes, On interference phenomena to be
expected when Röntgen rays pass through a di-atomic gas. Proceedings
Koninklijke Akademie van Wetenschappen 17: 1184-1190 (1915)

T. Sauer: A Look Back at the Ehrenfest Classification, PTCP2016 6

 Einstein’s co-author: S.B. Preuss ?

A. Einstein. 1931. Sitzber. Preuss. Akad. Wiss. ...

A. Einstein. Sitzber. Preuss. Akad. Wiss. ... (1931)
A. Einstein (1931). Sber. preuss. Akad. Wiss. ...
Einstein. A. 1931. Sb. Preuss. Akad. Wiss. ...
A. Einstein. S.-B. Preuss. Akad. Wis. ...1931
A. Einstein. S.B. Preuss. Akad. Wiss. (1931) ...
Einstein, A., and Preuss, S.B. (1931). Akad. Wiss. 235

folklore: google “S.B.Preuss”, on wikipedia

T. Sauer: A Look Back at the Ehrenfest Classification, PTCP2016 7

 1. Introduction

In its original format, the Ehrenfest classification scheme identifies the order of a phase
transition as that of the lowest derivative of the Helmholtz free energy which displays a discon-
tinuity there [1]. Typical transitions which fit to this scheme are first-order solid–liquid–vapour
transitions and second-order superconducting transitions. There are, however, many transitions
characterised by divergent rather than discontinuous behaviour. Examples include ferromag-
netic transitions in metals and the spontaneous symmetry breaking of the Higgs field in particle
physics, which display power-law or logarithmic divergent behavior as the transition is ap-
proached. The classification scheme has, in practice, been extended to encompass these scenarios
and the order of a transition is commonly given by the order of the lowest derivative in which
any type of non-analytic behaviour is manifest.

References

[1] P. Ehrenfest, Commum. Kamerlingh Onnes Lab. Leiden 20 (Suppl. 75B) (1933) 8.
[2] P. Kumar, D. Hall, R.G. Goodrich, Phys. Rev. Lett. 82 (1999) 4532.
[3] B.F. Woodfield, D.A. Wright, R.A. Fisher, N.E. Philips, H.Y. Tang, Phys. Rev. Lett. 83 (1999) 4622.
[4] P. Kumar, J. Low Temp. Phys. 106 (1997) 705.
[5] P. Kumar, A. Saxena, Philos. Mag. B 82 (2002) 1201;
P. Kumar, Phys. Rev. B 68 (2003) 064505.
[6] A.K. Farid, Y. Yu, A. Saxena, P. Kumar, Phys. Rev. B 71 (2005) 104509.
[7] T. Berlin, M. Kac, Phys. Rev. 86 (1952) 821.
[8] K. Kanaya, S. Kaya, Phys. Rev. D 51 (1995) 2404;
H.G. Ballesteros, L.A. Fernández, V. Martín-Mayor, A. Muñoz Sudupe, Phys. Lett. B 378 (1996) 207;
T. Sauer: A Look Back at the Ehrenfest Classification, PTCP2016 8
 [1] P. Ehrenfest, Commum. Kamerlingh Onnes Lab. Leiden 20 (Suppl. 75B) (1933) 8.
[2] P. Kumar, D. Hall, R.G. Goodrich, Phys. Rev. Lett. 82 (1999) 4532.
[3] B.F. Woodfield, D.A. Wright, R.A. Fisher, N.E. Philips, H.Y. Tang, Phys. Rev. Lett. 83

T. Sauer: A Look Back at the Ehrenfest Classification, PTCP2016 9

 KONINKLIJKE AKADEMIE VAN WETENSCHAPPEN
TE AMSTERDAM

PROCEEDINGS OF THE
SECTION OF SCIENCES

VOLUME XXXVI
(Nos. 1-5)

PUBLlSHED BY
N .V. NOORD-HOLLANDSCHE UITGEVERSMAATSCHAPPIJ.
AMSTERDAM. 1933

http://www.dwc.knaw.nl/toegangen/digital-library-knaw/

T. Sauer: A Look Back at the Ehrenfest Classification, PTCP2016 10

 Physics. - PhasenumwandlLlngen im Lleblichen Llnd erweiterten Sinn.
classifiziert nach den entsprechenden SingLllaritaeten des
dynamischen Potentiales. Von P . EHR ENfEST. Supplement N°. 75b
zu den Mitteilungen aus dem KAM ER LINGH Leiden.
(Comlllun i.:ated at thc mceti nÇJ o f Fchru<lry 25. 1933.)

ZUSAMMENFASSUNG.

Die Messungen von KEESOM und seinen Mitarbeitern ueber den charakteristischen
Verlauf der spezifischen Waerme des flu essigen Heliurns und auch der Supraleiter legen
es nahe. eine bestimmte Verallgemeinerung des Begriffes der Phasenumwandlung zu dis-
cutieren. Discontinuitaetscurven verschieden hoher Ordnung auf der Flaeche des thermo-
dynamischen Potentiales werden zu Uebergangscurven fuer die "Umwandlungen erster.
zweiter und hoeherer Ordnung zwischen zwei Phase n". Bei den ueblichen Umwandlungen
erster Ordnung ergibt sich zwischen den Spruengen der ersten Differentialquotienten des
thermodynamischen Potentiales. also zwischen S" - 5' und v" - v' die Gleichung von
Clapeyron . Bei denen der zwe iten Ordnung dazu anologe Gleichungen zwischen den
()v ()v
Spruengen der spezifischen Waerme und den Spruengen von ,)T und --;lp'

Die durch KEESOM mit seinen Mitarbeitern entdeckte. innerhalb der

bis jetztabstract
Titel and experimentelI
from Ehrenfest’serreichten Genauigkeit
1933 paper as published als Discontinuitaet
in the Proceedings of the Dutch Academy
sprechende Anomalie im Verlauf der spezifischen Waerme des f1uessigen
Heliums und die durch ihn mit CLUSIUS 2) studierte
T. Sauer: A Look Back at the Ehrenfest Classification, PTCP2016 11
 Phase transitions in the usual and generalized
sense, classified according to the singularities of
the thermodynamic potential.
P. Ehrenfest
Communicated at the meeting of February 25, 1933

Abstract
The measurements by Keesom and collaborators about the charac-
teristic function of the specific heat of liquid helium and also of the su-
perconductors suggest a certain generalization of the concept of a phase
transition. Discontinuity curves of different order on the surface of the
thermodynamic potential turn into transition curves for the “transitions
of first, second, and higher order”. For the usual phase transitions, we
obtain the Clapeyron equation between the jumps of the first differen-
tial quotients of the thermodynamic potential, i.e., between S ′′ − S ′ and
v ′′ − v ′ . For those of the second order, we obtain analogous equations
∂v
between the jumps of the specific heat and the jumps of ∂T and ∂v
∂p
.

T. Sauer: A Look Back at the Ehrenfest Classification, PTCP2016 12

 Paul Ehrenfest with son Pawlik and Albert Einstein in Ehrenfest’s home, ca. 1920
T. Sauer: A Look Back at the Ehrenfest Classification, PTCP2016 13
 From Einstein’s obituary for Ehrenfest
(1934)

This situation was made worse in his final years by the turbulent
development which theoretical physics has seen recently. To be
studying and teaching something that one does not accept
wholeheartedly, is a difficult thing to, doubly hard for a fanatically
honest mind for whom clarity was everything. This comes in
addition to the difficulties that adaptation to new ideas always
poses to the 50-year old. I do not know how many readers can
understand the tragic of these lines; but it was this tragic in the
first place which caused his escape from life.

T. Sauer: A Look Back at the Ehrenfest Classification, PTCP2016 14

 Paul Ehrenfest
(1880-1933)

born and raised in Vienna in a Jewish

family

studied in Vienna with Boltzmann,

then Goettingen (1901) where he met
his wife Tatyana Alexeyevna
Afanasyeva (1876-1964) whom he
married in 1904

back to St.Petersburg

became Lorentz’s successor as

professor of physics at the university
of Leiden in 1912

T. Sauer: A Look Back at the Ehrenfest Classification, PTCP2016 15

 Tatyana Alexeyevna Afanasyeva

(1876-1964)

came from Kiev

was a mathematician of her own
right
worked among other things on
the theory of dimensional
analysis, randomness, entropy
also wrote a textbook introducing
geometry for children

T. Sauer: A Look Back at the Ehrenfest Classification, PTCP2016 16

 In 1911, Paul and Tatyana Ehrenfest co-
authored the chapter on the conceptual
foundations of statistical mechanics for
Felix Klein’s encyclopedia of the mathematical
sciences (after Boltzmann had passed in 1906)

BEGRIFFLICHE GKUNDLAGE:N^
IV 32.

DER STATISTISCHEN AUFFASSUNG IN DER

MECHANIK. The paper became a
Von classical, was
P. u. T. EHRENFEST*) translated into
IN ST. PETEHSBURG.
English, and is still
Inhaltsübersicht.
available as a Dover
Vorbemerkung. reprint.
1. Einleitung.

I. Die ältere Fassung statistisch -mechanischer Untersuchungen (Kineto-

statistik des Moleküls).

2. Die ersten, vorläufigen Wahrscheinlichkeitsansätze.

3. Die Gleichhäufigkeit anscheinend gleichberechtigter Vorkommnisse.
a) Die Ansätze bei Clausius.
b) Der „Stosszahlansatz".
T. Sauer:4.A Die
LookRelativhäufigkeit
Back at the Ehrenfestnicht
Classification, PTCP2016
gleichberechtigter Vorkommnisse. 17
 Ehrenfest to J. Robert Oppenheimer

(summer 1928)

"If you intend to mount heavy mathematical artillery again during your
coming year in Europe, I would ask you not only not to come to Leiden,
but if possible not even to Holland, and just because I am really so fond
of you and want to keep it that way. But if, on the contrary, you want to
spend at least your first few months patiently, comfortably, and joyfully
in discussions that keep coming back to the same few points, chatting
about a few basic questions with me and our young people-and without
thinking much about publishing (!!!)-why then I welcome you with open
arms!! "

(quoted from his wikipedia entry)

T. Sauer: A Look Back at the Ehrenfest Classification, PTCP2016 18

 Ehrenfest’s
doctoral students
Johannes Martinus Burgers

Hendrik Casimir

Dirk Coster
Tatyana, mother and
daughter: T and T’ Samuel Goudsmit

Ehrenfest paradox Hendrik Kramers

“adiabatic principle” Reolf Krans

Arend joan Rutgers

Ehrenfest theorem
Jan Tribergen
“Gruppenpest”
Jan Tresling

George Uhlenbeck

T. Sauer: A Look Back at the Ehrenfest Classification, PTCP2016 19

 … Ehrenfest’s 1933 paper …

The anomaly in the dependence of the specific heat of liquid helium, which
was discovered by Keesom and collaborators1 and which under the currently
available experimental precision appears to be a discontinuity, as well as the
shift of this “lambda point” under pressure along a “lambda-point-curve” in
the p-T -plane studied by him together with Clusius2 justify the interpretation
of this curve as a transition curve between two modifications of liquid helium:
He I and He II, i.e. as a p, T -transformation curve between two (liquid) phases.—
It also fits with this interpretation that Keesom3 was able to derive a relation
between the jump of the specific heat, on the one hand, and the jump of the
thermal expansion coefficient, on the other hand, by means of considering a
cyclic process and to establish a satisfactory agreement with the measurements.

T. Sauer: A Look Back at the Ehrenfest Classification, PTCP2016 20

 Physics. - On the jump in the expansion coefficient of liquid helium in
passing the lambda-point. By W . H. KEESOM. Supplement No. 75a
to the Communications from the KAMERLINGH ONNES Laboratory
at Leiden.

(Communicated at the meeting of February 25 . 1933.)

Summary. A relation is derived between the inclination of the lambda-curve in the

P. T-diagram . the jump in the speci/ic heat. and the jump in the expansion coefficient.
This relation is used to calculate the expansion coefficient of Iiquid helium 11 at 2.19° K.
The value obtained is in harmony with the results obtained by KAMERLINGH ONNES
and BOKS in their measurements on the denslty of Iiquid helium .

§ I. Introduction. In the measurements on the anomaly in the spe-

cHic heat of liquid helium under its saturated vapour pressure. made in
collaboration with Miss A. P. KEES OM 1). it appeared that in the after-
period the galvanometer in the measurements above 2.19° K. had quite
a different course from those below 2.19° K. : comp. Fig . I of Comm .
No.
T. Sauer: A Look221d. TheClassification,
Back at the Ehrenfest explanation
PTCP2016 which readily presents itself for this pheno- 21
 Willem Hendrik Keesom
(1876-1956)
PhD student of J.D. van der Waals

student also of Heike Kamerlingh Onnes

slightly difficult career but in 1924 became co-director of the physics lab (with
deHaas)

published thereafter more than 200 papers in 20 years

studied dipole-dipole interactions in 1921

invented a method to solidify liquid helium in 1926 (Keesom interactions)

cooled helium down to 0.7K in 1927

discovered lambda transition point for specific heat curve for liquid helium at
2.19K

some work done together with his daughter Anna Petronella

T. Sauer: A Look Back at the Ehrenfest Classification, PTCP2016 22

 Heike Kamerlingh Onnes, Lars Vegard, and W.H.Keesom in the cryogenic
laboratory at Leiden

T. Sauer: A Look Back at the Ehrenfest Classification, PTCP2016 23

 The Onnes
Laboratory

Onnes was Prof at Leiden 


1882-1923

founded cryogenic lab in 1904

The Heike Kamerlingh Onnes Laboratory 1936
first liquified helium in 1908

remained the only lab capable of liquifying helium for 17 years (the “coldest place
on earth”), 1925 Toronto, 1930 Berlin, etc.

discovery of superconductivity in 1911

T. Sauer: A Look Back at the Ehrenfest Classification, PTCP2016 24

Resultaten zeigt, spiegelt die Abkühlungskurve in der Tat den Verlauf der
spez. Wärme bis in alle Einzelheiten wieder.
Die Physics.
Resultate
- von zwei
Ueber die Messtagen sind des
spezifische Wärme für flüssigen
die spez. Wärmen
Heliums. Von C. auf
W. H.
Fig. 3 vereinigt KEES
und OM allen
mit und K.wesentlichen
CLUSIU S. Communication
Unterlagen N0. 21ge fromTabellen
in den the 11
KAMERLINGH-ONNES Laboratory at Leiden. SPECIFIC HEAT OF LIQUID HELIUM IN ZERO . . .
und 111 niedergelegt. Am meisten fällt sofort das starke Maximum bei
2.19 0 K auf. Während sämtliche
(Communicated bis
at the her am
meeting Helium
of April 2. 1932.)beobachteten

lien nur als relativ geringfügige Effekte in Erscheinung treten, zeigt sich
§ I. Einleitung. Die spez. Wärme des flüssigen Heliums ist bereits
Gegenstand einer Untersuchung gewesen. DANA und KAMERLINGH
2.5 , -- - - - ,- -- - - ,- - - -- - - , -- - - - , - - - - ,
ONNES c 1) haben die spez. Wärmen beim Sättigungsdruck zwischen 4.05 °
und 2.611° K mitgeteilt und festgestellt . dass in diesem Temperaturbereich
der Verlauf der Messdaten
2.0 - ---j--- in erster -Näherung
- --+-"1- durch eine linea re Funktion
- --+------+----1
wiedergegeben werden kann.
Es war wünschenswert. unsere Kenntnisse über diesen Gegenstand zu
erwdtern und nach tieferen Temperaturen vorzudringen als es den
genannten Forschern möglich war. Dazu gab besonders der Umstand
Anlass. ,dass flüssiges Helium offenbar in zwei verschiedenen Zuständen
existiert. die bei etwa 2. I 9° K ineinander überzugehen scheinen 2).
Besonders dürfte man au eh erwarten durch Messungen der spezifischen
Wärme unter höherem Druck die dadurch verursachte Verschiebung des FIG. 17. Bin-averaged data close to the transition. Line shows
PHYSICAL REVIEW B 68, 174518 !2003"
Umwandlungspunktes messend verfolgen zu können. Zu dem Zweck
wurde das Kalorimetergefäss so konstruiert dass es die geplanten Drucke Specific heat of liquid helium in zero gravity very near the lambda point

auszuhalten vermag. J. A. Lipa,* J. A. Nissen, and D. A. Stricker

Physics Department, Stanford University, Stanford, California 94305-4085, USA
Äussere Umstände haben veranlasst. dass bis jetzt Messungen der
D. R. Swanson
spezifischen Wärme bei höheren Fig. 3 noch nicht haben stattfinden
Drucken Callida Genomics, Sunnyvale, California 94085-3513, USA

können . Dagegen hat der Verlauf der Umwandlungskurve aus bei ver- T. C. P. Chui
C• KEESOM
r::::Jschiedenen Drucken und aufgenommenen
CLUSIUS XAbkühlungskurven
DANA und KAMERLINGH
genügend ONNES.
fest-
Jet Propulsion Laboratory, Caltech, Pasadena, California 91109-8099, USA
!Received 10 April 2003; revised manuscript received 5 August 2003; published 14 November 2003"
8gelegt Cp
werden können. Die in dieser Hinsicht gewonnenen Daten sind We report the details and revised analysis of an experiment to measure the specific heat of helium with

schon publiziert worden 3).

Wir hatten auch gehofft die bezüglich der spezifischen Wärm en unter
Sättigungsdruck erhaltenen Daten noch durch weitere Messungen zu ver-
vollständigen. Weil diese geplante Fortsetzung der Arbeit aber jedesmal
verschoben werden musste. glauben wir jetzt die Veröffentlichung nicht
länger aufschieben zu dürfen.

§ 2. Beschreibung d er Apparatur. Fig . 1 vermittelt eine Anschauung

von den wesentlichsten Teilen der Apparatur. bei deren Aufstellung die in
T. Sauer: A Look Back at the Ehrenfest Classification, PTCP2016 25
 phenomenon: decrease of the heat transport through the liquid, possib

one may conclude that the true specific heat at 2.201 ° K probably surpasses
1.1 ,Jery little. if at all. The same conclusion is arrived at by an analysis of
Physics. - On the Anomaly in the Specific Heat of Liquid Helium. By
experiment I h of the same day. To explain the average specific heat
W. H. KEESOM and Miss A. P. KEESOM. Communication N0. 221d & found
in this fromexperiment
the KAM ERLlNG I-I one
O NNESmust moreover
Laboratory at Leiden. assume that the jump in the specific

heat must have occurred very shortly af ter the reading of 440;( m 20 sec
\5 I
(Communica ted a t the meeting of Jun e 25. 1932) . 10 / 0
(cf. Fig. I) . and must have been completed within some thousandths V of a
§ I . Introdu ction. The investigation on the specific heat of liquid
degree. os 0 '"'
l!.
A

helium made by one of us with Dr. CL US IUS ,) gave rise to some questions
So our conclusion is that the specific
which made a nearer investigation of the anomaly of the specific heat of heat o
\2
of I &'"
liquid
T l4 helium at about
la '.8 2.0 2.2 24 2.6 2.8

that substance. revealed by t he investigation mentioned . desirabIe. Fig . 2

2.19° K faBs from a value of 3.0 to a value of about
So it seemed important to see whether the curve of the specific heats
A 1.1 certainly
April 21st. o within
o
April 28th. KEESOM and CLUSIUS.

0.02
obtaineddegree . very
should und probably
er go some change if even
a betterwithin a couple
heat conduction in the of thousandths of a degree.
liquid was provided for. In this connection the course of the curve of the
b. Leaving open the question whether the fall of the specific heat really
specific hea ts above 2.19 K attracted special attention. Although we have
0

occurs
not yet been discontinuously
able to make experiments in the strict
in which sen se of
the conditions of heat
the word. or in a very sm all
supply and hea t conduction were the most ideal on.es. we could make some
temperature
measurements with interval.
improved heatitconduction
will bein the appropriate
liquid in such a from
way an experimental point of
that we can
view to draw a t leas t a preliminary
consider the fallconclusion
to occur concerning this question.For convenience sake it is
abruptly.
desirabIe
') W . H. KEESOMtoandintroduce
K. CLUSIUS. Thesea Proceedings.
name 35.for the Comm.
306. 1932; point Leidenat which this jump occur&.
No. 21ge.
According to a suggestion made by Prof. EHRENFEST we propose to call
that point . considering the resemblance of the specific heat curve with the
Greek letter J.. the lambda-point.
The curve that shows how the lambda-point depends on the pressure will
be called the lambda-curve 1) .
As in several cases it is also convenient to distinguish between the two
T. Sauer: A Look Back at the Ehrenfest Classification, PTCP2016 26
 It appears that Ehrenfest introduced the notion of phase
transitions of different order as a reflection on the curious
phenomenon of the lambda point maximum in the specific heat
of liquid helium.
Fine. But:
This is remarkable, because the lambda transition is actually a
bad example since there is no jump in the specific heat but a
divergence.
and:
the superfluidity of He II had not even been discovered, yet.

T. Sauer: A Look Back at the Ehrenfest Classification, PTCP2016 27

 “Unlearning” physics: 

what did Ehrenfest not know in 1933?
virtually nothing about spin models (Lenz 1920, Ising 1925, Heisenberg 1928, Bloch 1932,
Onsager 1944)

superfluidity of He II discovered by Keesom and daughter in 1936 and by Kapitza et al 1938

almost nothing about SC except for that a a critical temperature many materials experience a
sudden loss of resistivity (Meissner-Ochsenfeld effect 1933)

Ginzburg-Landau theory

renormalization group theory

but a lot of empirical knowledge and theoretical models on magnetism and equation of states

sorting out the chronology of “filling in the picture” is part of historical research

T. Sauer: A Look Back at the Ehrenfest Classification, PTCP2016 28

 … Ehrenfest’s 1933 paper …

cyclic process and to establish a satisfactory agreement with the measurements.

Because of the suggestive similarity with a phase transition it is all the more
interesting to take a closer look also at the characteristic dissimilarity: this is
the absence of an entropy difference (latent heat) and of a volume difference
between these two phases.

T. Sauer: A Look Back at the Ehrenfest Classification, PTCP2016 29

 … Ehrenfest’s 1933 paper …

In a very instructive discussion, in which Keesom directed my attention

to these circumstances, it became evident that one can formulate the peculiar
generalization of the concept of a phase transition which is suggested by the
discovery of the lambda-point-curve very conveniently in the language of the
thermodynamic potential of the zeta function Z(T, p). I believe to be justified
in following Keesoms suggestion to publish these remarks because an analogous
kind of formulation will likely prove to be convenient for the behavior of su-
perconductors at the jump temperature and of the ferromagnets at the Curie
temperature. 154

In der fuer mich sehr lehrreichen Discussion. in der KEESOM meine

Aufmerksamkeit auf diese Vorkommnisse lenkte wurde sichtbar. dass man
besonders bequem in der Sprache des thermodynamischen Potentiales
der Zetafunction Z (T. p) die eigenthuemliche Erweiterung des Begriffes
T. Sauer: A Look Back at the Ehrenfest Classification, PTCP2016
Phasenumwandlung formulieren kann. die durch die Entdeckung 30 der
 … Ehrenfest’s 1933 paper …
154

In der fuer mich sehr lehrreichen Discussion. in der KEESOM meine

Aufmerksamkeit auf diese Vorkommnisse lenkte wurde sichtbar. dass man
§ 1. Singular curves of different order on the
besonders bequem in der Sprache des thermodynamischen Potentiales
der Zetafunction Z (T. p) die eigenthuemliche Erweiterung des Begriffes
Z(T, p)-surface Phasenumwandlung formulieren kann. die durch die Entdeckung der
Lamda-Punkt-Curve nahegelegt wird. Der Aufforderung Herrn KEESOMS
I begin by recalling the die betreffenden
following Bemerkungen zu publizieren glaube ich folgen zu duerfen.
equations
weil wahrscheinlich auch fuer das Ver halten der Supraleiter bei der Spung-
temperatur ∂Z
und der Ferromagnetika bei der Curietemperatur eine analoge
= −Ssich als bequem erweisen wird.
Art von Formulierung (1)
∂T
§ 1. Singulaere
∂Z Curven verschieden hoher Ordnung auf der Z (T. p)-
=v
Fla eche. Es sei zunaechst an folgende Formeln erinnert : (2)
∂p
àZ
2
∂ Z ∂S C oT =
- S. (1)
2
=− =− (3)
∂T ∂T T àZ
- = v (2)
∂2Z ∂v op
= (4)
∂p ∂p à2 Z àS C
(3)
2 à P - -à T - T '
∂ Z ∂S ∂v
=− =− ,2 (5)
∂T ∂p ∂p ∂T à Z àv
(4)
Op2 - op
where Z(T, p) denotes the thermodynamic potential, S the entropy, c the specific
à2 Z
heat at constant p. In general, Z(T, p) is continuous oS allàvlower differential
- with
- ar; (5)
àTop àT

wo Z
T. Sauer: A Look Back at the Ehrenfest Classification, PTCP2016 (T . p) das thermodynamische Potential. S die Entropie. c die
31
 à2 Z àS C
(3)
à P - -à T - T '

… Ehrenfest’s 1933oppaper … à2 Z
Op2 -
àv
(4)

à2 Z oS àv
àTop
- - ar; àT
(5)
quotients. But now let us look at a piece of a “transition curve” in the p, T -plane,
where discontinuities are found
wo Z that will
(T . p) dasbethermodynamische
discussed below.
Potential. S die Entropie. c die
spezifische Waerme bei constantem p
ist. Im allgemeinen verlaeuft Z (T. p)
mit allen niedrigen Differentialquo-
tienten stetig . Doch sei nun ein Stueck
einer .. U mwandlungs-Curve" in der
p . T - Ebene betrachtet. an der naeher
zu besprechende Discontinuitaeten vor-
liegen.
Jedenfalls koennen wir einen Sprung
von Z selber ausser Betracht lassen.
Das heisst jedenfalls soll laengs der
ganzen Uebergangscurve A. B geiten :
T z. - ZI - ((Z))=O . (I)
denn ein Sprung von Z wuerde ja wegen -1. 2 ein unendlichwerden von
In any case, we can disregard theEntropie
Volumen und possibility of. a jump of Z itself. This
bedeuten
means that in any case we have along the entire transition curve A, B:
Zr − Zl = ((Z)) = 0. (I)

T. Sauer: A Look Back at the Ehrenfest Classification, PTCP2016 32

 … Ehrenfest’s 1933 paper …
With a discontinuity of second order, however, we shall have
!! "" !! ""
∂Z ∂Z
(I) ((Z)) = 0 (II) =0 (III) =0 (8)
∂T ∂p
and only then
2
!! ""
∂ Z ((c))
2
=− ̸= 0 (9)
∂T T
!! 2 "" !! ""
∂ Z ∂v
2
= ̸= 0 (10)
∂p ∂p
!! 2 "" !! "" !! ""
∂ Z ∂v ∂S
= =− ̸= 0 (11)
∂T ∂p ∂T ∂p

(cp. 3, 4, 5). The relationship (9) shows that such a discontinuity is the case
just with Keesom’s lambda-point-curve, where the specific heat is discontinuous
but we still have Q = 0 and ((v)) = 0.

T. Sauer: A Look Back at the Ehrenfest Classification, PTCP2016 33

 … Ehrenfest’s 1933 paper …

§ 2. Clapeyron’s equation and the analogous re-

lations in the case of phase transitions of higher
order
Dp Q
[1st order:] =
DT T (vr − vl )
## ∂S $$
Dp ∂T ((c))
[2nd order:] = − %% && = ## ∂v $$
DT ∂S T ∂T
∂p
## $$

T. Sauer: A Look Back at the Ehrenfest Classification, PTCP2016 34

 … Ehrenfest’s 1933 paper …

%% &&

§ 3. Some remarks
a. Our considerations only refer to the occurrence of discontinuities in the
specific heat.4 We did not comment on the possible occurrence of “bumps”5 in
their dependence. These one would want to treat as something like an unsharp
phase transition.

T. Sauer: A Look Back at the Ehrenfest Classification, PTCP2016 35

 … Ehrenfest’s 1933 paper …

b. Although we believe it to be useful to talk about “transformation of one

phase into another one” also in the case of discontinuities of second order, it does
not seem to be possible in this case to have both phases “spatially coexistent”
in equilibrium. I would wish very much that I were capable of formulating
and understanding this characteristic difference with respect to “usual” phase
transformations in a better way.

T. Sauer: A Look Back at the Ehrenfest Classification, PTCP2016 36

 … Ehrenfest’s 1933 paper …

c. Here one feels especially well the kinship with the transformation into the
superconducting state and into the ferromagnetic state. In the latter case, by
the way, we don’t seem to be dealing with a t, H-discontinuity curve but only
with a point: H = 0, T = tc .

T. Sauer: A Look Back at the Ehrenfest Classification, PTCP2016 37

T. Sauer: A Look Back at the Ehrenfest Classification, PTCP2016 38
T. Sauer: A Look Back at the Ehrenfest Classification, PTCP2016 39
 Thank you for your attention

T. Sauer: A Look Back at the Ehrenfest Classification, PTCP2016 40