On the Thermodynamics of the Critical Region for the Ising Problem

G. S. Rushbrooke

Citation: J. Chem. Phys. 39, 842 (1963); doi: 10.1063/1.1734338

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 842 LETTERS TO THE EDITOR

proved the existence in ethanol of a second dispersion
by studying this substance at lower frequencIes and
low temperatures.
In the case of n-alcohols between C6 and C12 , one of
us has shown7 that there also exists a third dispersion
region with, for example, in n-octanol, a critical wave-
length at 5 mm (a result confirmed by Rampolla,
Miller, and Smyth8). An analogous third region h~s
F. W. Heineken and F. Bruin, Physica 23, 57 (1957).
6
F. X. Hassion and R. H. Cole, J. Chern. Phys. 23,1756 (1955).
6
7 C. Brat, Ann. Phys. (Paris) 13-2, 714 (1957).
"R. W. Rampolla, R. C. Miller, and C. P. Smyth, J. Chern.
Phys. 30, 566 (1959).
9 R. Arnoult A. Lebrun C. Moriamez, M. Moriarnez, and R.
Wernelle, Arch: Sci. (Gene~a) Fasc. Special, 6e Colloque Ampere,
10,48 (1957). . ".,
10 M. Moriamez, Arch. SCI. (Geneva) I·asc. SpeCIal. 7c Colloflue
Ampere, 11, 90 (1958).
11 E. Bauer, Cahiers Phys. No. 20,1; No. 21, 21 (1944).

later been found in other isomers of octanol 9 and m 12 M. Moriamez, thesis, University of LilIe, 1959.
13 R. Liebaert, thesis, University of Lille, 1962.
cyclohexanol,1O to mention only monoalcohols.
The existence of such a plurality of dispersion regions,
which appears to be of general character in alcoh~ls,
calls for a physical interpretation. The one whlCh
seems now rather widely admitted is based upon Dispersion at Millimeter Wavelengths in
H-bonded molecular association, contrary to the Methyl and Ethyl Alcohols
opinion of Saxton et al. Briefly, this interpretation is J. A. SAXTON
as follows: Polymers of variable length exist in the
Radio Research Station, Slough, Bucks, England
liquid-together with free molecules-all in ~ynamicaJ
equilibrium. The lifetime T of an H bond IS smaller (Received 28 March 1963)
than the time necessary for all but the very shortest
AM grateful to Brot and Magat for drawing my
polymers to reorient themselves as a whole in the ap-
plied field; it is the breaking of an H bond ~hat makes
I attention to recent work on dispersion in methyl
and ethyl alcohols, some of which, because of its difficult
possible the orientation of the liberated dIpoles. liT
accessibility, had escaped the attention of my col-
consequently corresponds to the frequency of the main
leagues and myself at the University of Texas. l In
dispersion region. 3 ,ll This region does not prese~t ~ny
discussing the comments made by Brot and Magat2
distribution of relaxation times because the hfetIme
mention may also be made of work by Grant,3 whose
of the H bonds is roughly independent of the size of
accurate measurements in the wavelength range 3 to
the polymer. The interpretation of t~e se~ond r~gion, 52 cm have shown that the main dispersion region in
which shows a distribution of relaxatlOn tImes, IS Jess
each alcohol can be characterized by a single relaxa-
certain. It might be due to the orientation as a whole
tion time. The evidence referred to by Brot and Magat
of very short polymers (dimers for example). Another
essentially confirms the phenomenological explana-
contribution might arise from the orientation of ~he
tion of the behavior of the two alcohols advanced by
smaller dipoles OC (along the hydrocarbon cham)
Saxton4 in 1952 and supported by the recent measure-
inside a polymer, without breaking of the H bond.&·7
ments at millimeter wavelengths. l It is of course pos-
Finally, the third domain has been interpreted by ~S7
sible that the theories described by Brot and Magat
as a resulting from the orientation of molecules w~lch
do in fact account for the physical processes associated
are at a given instant, either free or at a termmal
with the different dispersion regions but, unfortu-
po;ition of a polymer. This hypothesis is borne out by
nately, it is usually much easier to prove that a theory
the fact that an increase of temperature,? as well as
is wrong than that it is right.
a dilution in an inert solvent,7,lO,l2,l3 give rise to an
increase of the relative amplitude of this third region. 1 J. A. Saxton, R. A. Bond, G. T. Coats, and R. M. Dickinson,

This interpretation provides a basis for determining 7 J. Chern. Phys. 37, 2132 (1962).
2 C. Brat and M. Magat, J. Chern. Phys. 39,841 (1963).
the thermodynamics and kinetics of the association 3 E. H. Grant, Prac. Phys. Soc. (London) B70, 937 (1957).
considered, as well as to make an a priori calculation I J. A. Saxton, Proc. Roy. Soc. (London) A213, 413 (1952).
of the correlation factor g to the static polarization,
which is in correct agreement with experimental values. 7
In conclusion, the existence of a secondary disper-
sion region in methanol and ethanol was somewhat to On the Thermodynamics of the Critical
be expected; moreover, it seems likely that, as in other Region for the Ising Problem
alcohols, a third region exists, perhaps at, or under,
A=l mm at room temperature. G. S. RUSHBROOKE*

Chemistry Department, University of Oregon, Eugene, Oregon

J. A. Saxton, R. A. Bond, G. T. Coats, and R. M. Dickinson,
1
(Received 1 April 1963)
J.Chern. Phys. 37, 2132 (1962). . .
• R. Dalbert, M. Magat, and A. Surdut, p'olar.tsatwn de fa
HE recent paper by Essam and Fisherl which,
matiere (Centre National de la Recherche SClentJfique, Pans,
1949). . II 'd Z 134 , 101
3 C. Brat, M. Magat, and L. Reimsch, Ko OJ - .
T inter alia, reports numerical work, by Pade approxi-
mants, on the nature of the specific heat and suscepti-
(1953) .
4 A. Lebrun, Ann. Phys. (Paris) 10, 16 (1955). bility singularities for the Ising problem, on the low-

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 LETTERS TO THE EDITOR
temperature side of the Curie temperature, allows us
to test the thermodynamic formula
T(aM/aT)2H
(1)
(aM/aH)T
in the case H =0 and T less than, but approximately
equal to, Te. The equation itself, of course, is not in
doubt: it is simply the more familiar formula for Cp -
Cv when the work term pdV is replaced by the work
term-HdM, where H is the magnetic field and M
the magnetization of the system. The only question is
whether (1) yields useful information.
At H=O, (aM/aT)H is the slope of the magnetic
phase boundary, M(T), and (aM/aHh is the zero-
field susceptibility, x. Likewise CH is then the zero-
field specific heat. Using the notation of Essam and
Fisher, we may suppose that for T less than but ap-
proximately equal to T e,
M(T) behaves like (Te- T)fl,
and
x(T) behaves like (Tc- T)-Y'.
The right-hand side of (1) then behaves like (Tc- T)-'
where ~=2-2{3-,,'. If ~::;O, Eq. (1) tells us nothing
about CH other than that CH and CM have equal
singularities. On the other hand, should we find E>O
then, since CM is necessarily positive (being essentially
a mean-square energy fluctuation) we can conclude
that CH has a singularity at Tc at least as strong as
(Tc- T)-'. In the notation of Essam and Fisher, CH
behaves like (T c - T)-a', and a logarithmic singularity
may be regarded as corresponding to a' =0. We thus
infer
a' + 2{3+,,' ~ 2 (2)
as a thermodynamic necessity: in contrast to the
equation
a' + 2{3+,,' = 2,
which Essam and Fisher derive heuristically from a
simple model.
For two-dimensional lattices we know rigorousli
that {3 = 1/8. The work of Essam and Fisher gives
,,' = 7/4. In this case E= 0, and the known logarithmic
singularitya in CH is not in conflict with Eq. (1);
indeed, Eq. (1) and the known logarithmic singularity
in CH allow us to infer ,,' ~ 7/4.
For three-dimensional lattices the situation is more
interesting. Originally Baker4 proposed the value 0.3
for the index {3, but Essam and Fisher make a strong
case for {3 = 5/16. Essam and Fisher also favor ,,' = 5/4,
the same index as on the high-temperature side of the
susceptibility singularity (for which see Baker4).
Adopting these values we find ~ = 1/8, i.e., a';::: 1/8. On
the other hand, Baker5 presents fairly strong evidence
for a'=O (a logarithmic singularity in CH ). There
would seem to be a definite conflict here with thermo-
dynamic requirements.
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843
There are two possibilities: either the specific heat
singularity is not logarithmic, or ~=O [in which case
we can infer nothing about the specific heat singularity
from Eq. (1)]. Keeping {3=5/16, ~=O demands
,,' = 11/8, as distinct from the exponent 10/8 on the
high-temperature side of the susceptibility singularity.
Although this lack of symmetry is esthetically dis-
pleasing, for the body-centered cubic lattice a value of
,,' as high as 11/8 does not seem to be ruled out by
Essam and Fisher's numerical data (Table IV of their
paper). For the simple cubic and face-centered lattices,
however, so high a value for,,' seems unlikely. The dis-
crepancy will probably not be finally resolved until
more adequate estimates of a' are practicable.
I am indebted to Dr. Baker for discussion and to
Dr. Fisher for correspondence on this matter.
* On leave of absence from King's College, Newcastle upon
Tyne, England, and indebted to the National Science Founda-
tion for financial support.
1 J. W. Essam and M. E. Fisher, J. Chern. Phys. 38, 802 (1963).
2 C. N. Yang, Phys. Rev. 85,808 (1952).
3 L. Onsager, Phys. Rev. 65, 117 (1944).
4 G. A. Baker, Phys. Rev. 124, 768 (1961).
5 G. A. Baker (preprint, 1962); see also A. J. Wakefield, Proc.
Cambridge Phil. Soc. 47,799 (1951).
Notes
Vibrational Spectra of Molten Mercuric
Halides. III. Mercuric Chloride-Thallous
Nitrate Mixtures
GEORGE J. JANZ AND THEODORE R. KOZLOWSKI
Rensselaer Polytechnic Institute, Department oj Chemistry,
Troy, New York
(Received 7 March 1963)
HE vibrational spectra of mercuric chloride as a
T pure one-component fused salt and in potassium
chloride mixtures have been reported elsewhere.! The
vibrational assignments are in accord with the evidence
from related physicochemical studies2 showing that the
mercuric halides form truly "molecular" liquids on
fusion, but in the presence of excess ligands such as
chloride ions (added as KCI) the linear triatomic
mercuric halide species transform to the more com-
plex HgXa- and HgXr anionic species. Precise cryo-
scopic measurements for HgCb and HgBr2 in thallous
nitrate have been recently reported. a These solutes are
observed to have values of the freezing-point depres-
sion close to the simple one for molecular solution.
This was shown to be in accord with the general ther-
modynamic theorem4 relating to the relative free en-
ergies of the four salts that can be regarded as compo-
nents of an ionic solution containing two anions and
two cations. The double decomposition reaction
!HgCb+TINOa=TICI+!Hg(NOa)2, results in a large
increase in free energy, and the thermodynamic fore-