HYDROGEN PEROXIDE: THE LOW TEMPERATURE HEAT

CAPACITY OF THE SOLID AND THE THIRD

LAW ENTROPY1

, L1U2p3,J. S. DUG DALE^,

BY PAULA. G I G U ~ R EI.~D.
AND J. A. MORRIS ON^

ABSTRACT
The heat capacity of crystalline hydrogen peroxide between 12" I<. and the
melting point has been determined with a low temperature adiabatic calorimeter.
T h e heat of fusion was also measured and found t o be 2987 f 3 cal./mole.
T h e two samples of hydrogen peroxide used were 99.97 mole % pure as deduced
from behavior on melting and from premelting heat capacities; the triple point
was estimated t o be 272.74" I<.
The only anomaly observed it1 the heat capacity measuren~entswas the
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absorption of 1.3 cal./mole a t 216.8 f 0.15" K., the lower eutectic temperature
of H20-Hg02 solutions. Such a n effect is t o be expected if the only significant
impurity is water. T h e entropy of hydrogen peroxide a s a n ideal gas a t 1 atm.
pressure and 25" C. computed from the thermal measurements is 55.76 f 0.12
cal./mole deg. Comparison of this datum with the recalculated statistical entropy
leads t o a value of 3.5 kcal./mole for the height of a hypothetical single barrier
hindering internal rotation in the molecule. From these results it is c o n c l ~ ~ d e d
t h a t hydrogen peroxide does not consist of two tauton~ericmodifications.

INTRODUCTION
Knowledge of the thermal properties of solid hydrogen peroxide has hitherto
been fragmentary and uncertain (15, 5). T h e accurate determination of the
heat capacity of the compound in the solid state down to low temperatures
was considered to be of special interest, primarily because it would make
possible a calculation of the third law entropy. An X-ray investigation of t h e
crystal structure of hydrogen peroxide ( I ) has shown that i t should not retain
any appreciable residual entropy a t the absolute zero. On the other hand,
evaluation of the statistical entropy of the ideal gas from structural a n d
spectroscopic d a t a (7) is hampered by the lack of sufficie~ltinfor~nationon
the internal rotation of the two OH groups in the molecule. The potential
barrier restricting that motion is expected to have two unequal inaxima (22).
which makes difficult a rigorous calculation of the contribution of that internae
degree of freedoin to the various thermodynamic functions. Another important
point is the question of whether transitions (18) and tautomeric forllls (6) of
hydrogen peroxide exist in the solid state (cf. Discussions of the Faraday
Society, 14: 140-142. 1953).
Because of the tendency of hydrogen peroxide t o decompose spontaneously
in contact with rilost materials, the project held certain experimental diffi-
culties. For convenience, the work was divided between two laboratories, o n e
1 firanuscript received November I S , 1953.
Joint contribulio7~from the Department of Chemistry, Laval University, Quebec, Quebec,
and the Division of Pure Chemistry, National Research Cozcncil, Ottawa, Carrada. Issued as
N.R.C. No. 3158.
Laval University.
Holder of a Fellowship from the Bureau of Scientific Research of the Province of Quebec-
4 National Research Laboratories Postdoctora& Fellow.
National Research Laboratories.
 118 CANADIAN J O U R N A L OF CHEdIISTRY. V O L . 32

a t Lava1 University where facilities existed for preparing the samples of pure
hydrogen peroxide and for sealing thein in suitable containers, and the other
a t the National Research Council where the calorimetric meas~u-ei-r-rentscould
be made.
EXPERInilENTAL
T h e Preparation of the Samples
T h e starting material for preparing the pure hydrogen peroxide was the
very stable goy0 solution supplied by the Buffalo Electro-Chemical Company.
Some six liters of this solution was concentrated to about 99.60Jo hydrogen
peroxide by clistillation a t reduced pressure through a 1 meter fractionating
column filled with sinall glass helices ancl heated electrically to prevent
flooding. Extensive precautions were taken t o avoid contamillation of the
solution. All glassware was treated with fuming sulphuric acid following the
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procedure recommended by Huckaba and Keyes (11). The still was assei-nbled
through ground glass-joints on which only a trace of silicone grease was used.
A fritted glass disc was placed on the vacuum line to filter off all dust particles
from the air let in after a distillation.
Further concentration of the peroxide was achieved by fractional crystal-
lization as described elsewhere (4). The apparatus was made simpler by using
a straight filtering tube with the two flasks connected a t each end. For sepa-
rating the solid from the mother liquor the whole assembly was merely turned
upside down and then suction was applied a t the outlet tube. T h e entire
operation was rendered still more effective by growing a single large crystal
instead of a mass of tiny ones. T o this end the flask filled with some 700gm.
of concentrated peroxide solution was wrapped in a thick glass-wool lagging
before it was placed in an ice machine a t - 10' C. Crystallization was initiated
by seeding and it proceeded very slowly (two days for solidification of about
goy0 of the sample). The progress of purification was followed by measuring
the freezing point (4) which did not change further after three or four opera-
tions.
T h e Calorimeter Vessels
Having once prepared the pure hydrogen peroxide it was important t h a t
i t should not come in contact with anything except very inert materials such
as specially treated glass or pure aluminum. For this reason and because
glass-to-aluminum seals are not available, the calorimeter vessels were made
entirely of pure (IS) aluminum. As will be seen from Fig. 1, the coilstruction
was such that no soldering or brazing was used. T h e tapered re-entrant well
in the base of the calorimeter receives the thermometer-heater assembly.
With this design the thermometer may be attached after the filling of the
calorimeter is completed. T h e resistance thermometer and calorimeter heater
were cast with Wood's metal into a tapered brass tube which fitted closely
the tapered re-entrant well. T h e brass tube was held firmly in place with
a threaded collar which screwed into the bottom of each vessel. Thermal
contact between the brass tube and the well was enhanced b y a light film of
silicone grease.
 A R C WELD

ALUMINUM

WOODS METAL

t:I INCH
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WELD

FIG.1. Aluminum calorimeter vessel. 1. Point of attachment of difference thermocouple.

2. Tapered brass tube. 3. Platinum resistance thermometer. 4. Anchoring ring for lead
wires and radiation shield.

T h e Filling of the Calorimeter Vessels

Although special precautions were taken in assembling the caloriilleter
vessels, their inside surfaces needed extensive passivation treatment before use.
This long and tedious operation involved the following steps. The metal was
first degreased by rinsing with acetone and then treated for a few minutes
with a 3y0 solution of sodium hydroxide followed b y numerous rinsings with
distilled water. Thereafter each vessel was filled with 25% nitric acid, allowed
to stand for several hours, and washed again thoroughly with distilled water.
Finally, repeated fillings with solutions of hydrogen peroxide of increasing
concentration from 30% to 99% over a period of a few weeks brought the
surfaces to a satisfactory level of inertness in the case of three out of the six
vessels originally made. The rate of decomposition of 99y0hydrogen peroxide
in these was of the order of 0.001% in 24 hr. a t room temperature and less
than one tenth of this a t 0°, which was deemed entirely safe.
After prolonged evacuation for drying, the vessels were filled with helium
gas a t atmospheric pressure for better thermal concluctivity, and the pure
liquid peroxide was poured in directly. A temporary closure was effected a t
once by pinching off the thin filling tubes, and after the vessels were accurately
 120 CANADIAN J O U R N A L OF CHEMISTRY. V O L . 32

weighed, the tubes were welded in an argon arc with the coritainers ilnlnersed
in ice water to prevent decomposition of the peroxide. They were then cooled
gradually to the temperature of dry ice and were kept a t this temperature
during transport to the National Research Laboratories in Ottawa. I t was
assumed that the rate of deconlposition of the frozen peroxicle would be
negligible, and this was co~lfirmedby the subsequent experiments. At no time
during the experiments was there any sign of thermal effects due to decoinpo-
sition of the hydrogen peroxide.
The Cryostat
T h e cryostat used for this work was similar to one already described in a
previous publication (20). Adiabatic operation was possible over the entire
temperature range from 11" K. The design of the cryostat proved to be
particularly convenient for mounting the calorimeter vessel without melting
the sample of hydrogen peroxide. By careful arrangement of the procedure it
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was possible to assemble the cryostat in about an hour, during which time the
temperature of the calorimeter vessel rose from that of dry ice to about - 5" C.
T h e &Ieasurements
T h e resistance of the platinum thermoineter and the energy supplied to the
calorimeter were measured after the methods which have become standard
for this type of worlc (26). All of the measurements were made with a White
double potentiometer. T h e standard resistors and standard cells have been
checlced periodically against standards maintained by the Division of Physics
of the National Research Laboratories. Time of input of energj7 to the calori-
meter was determined with a synchronous cloclc operated from a constant
frequency power supply through a switch coupled directly to that controlling
the heater current. T h e indications of the clock have been checked many times
by comparison with the time signals from the Doininion Observatory. T h e
error in the clock has never exceeded 0.02 seconds. Platiiluill resistance
tliermometer T-3 was used for this worlc. T h e calibration of this thermometer
has been described elsewhere (14).
RESULTS
The Heat Capacity
Of the three different samples of hydrogen peroxide prepared in separate
calorimeter vessels only two were used for the measurements (containing
3.3706 and 2.9175 moles respectively). Since it was not known beforehand
whether or not the peroxide would decompose appreciably on melting (8),
it seemed preferable to measure the heat capacity with one sample and the
heat of fusion with the other.
T h e results are given in Table I as smoothed values of the heat capacity a t
rounded values of the temperature. (In all the calculations the calorie was
taken equal to 4.184 absolute joules). T h e difference plot in Fig. 2 shows the
deviations of the experimental results from a smooth curve. I t will be noted
that over most of the temperature range the mean precision was better than
0.1%; below 30" K. the uncertainty was greater (of the order of 0.3%).
 TABLE I
THEHEAT CAPACITY OF SOLID HYDROGEN PEROXIDE
I II I

cal./mole deg. cal./mole deg.

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Marked prenrelting.

Premelting of the solid became evident around 250" K. as illustrated in

Fig. 3. A few measurements of the heat capacity of the second sample made
in the region above 250" I<. yielded results indistinguishable from those
obtained with the first sample. T h e dotted line in Fig. 3 represents the heat
capacity of pure solid hydrogen peroxide estimated as described below. Calcu-
lations showed t h a t the correction to be applied for evaporation into the dead
space of the calorimeter was negligible.
During the heat capacity measurenlents on the first sample a small ab-
sorption of energy was detected around 217" K. T h e amount of heat involved
seemed to depend upon the extent t o which the calorimeter had been cooled
previously. After cooling to temperatures below 77" K., the energy amounted
to 3.4 cal. while with cooling to around 200" K. it was only 1.9 cal. An attempt
was made to determine the temperature region over which this energy was
absorbed by following the temperature of the calorimeter while it received
energy a t a constant rate from its surroundings. From this experiment i t
appeared that the heat was absorbed between 216.78" and 216.94" K. T h a t
+ this effect was due to the melting of an eutectic mixture of hydrogen peroxide ,

and the addition compound H202. 2H2O is suggested by two facts. First, the
temperature region is very close to the eutectic temperature reported by
Foley and Giguitre (216.7" K. (4)). Second, assuming the eutectic mixture to
be an ideal one and the inlpurity present (0.032 mole yo-see below) to be
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TEMPERATURE, *K.
FIG.2. Deviations of experimental heat capacities fro111 a smooth curve.
entirely water, the calculated energy to be expected a t theeutectic temperature
is 3.9 cal., which agrees very well with the maximum amount found experi-
mentally.
Apart from this absorption of energy, no other anomalies were observed.
I t is estimated that a t the higher temperatures any transition involving an
energy greater than 0.1 cal./mole concentrated in a teinperature interval of
4" or less would be detected in these measurements; a t the lower temgeratures
even smaller quantities are detectable.
The Ileat of Fusion
T h e heat of fusion of hydrogen peroxide was determined by measuring the
energy required to heat the calorimeter and the second sample over a tempera-
ture interval which included the triple point. From this quantity was sub-
tracted the energy required to heat ( a ) the pure solid up to the triple point,
(b) the liquid from the triple point to the final temperature, and ( c ) the calori-
meter vessel from the initial to the final temperature. T h e premelting energy
is then included in the heat of fusion. T h e value so obtained was 2987 f 3 cal./
mole which may be compared with 2920 cal./mole determined by Foley and
Gigu6re ( 5 ) using an ice calorin~eter.T h e latter value is based upon a rather
uncertain estimate of the heat capacity of the solid just below the melting
point. However, using the corrected heat capacity of the solid does not remove
the discrepancy.
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FIG.3. The heat capacity of solid hydrogen peroxide in the premelting region.
0- Sample 1. - Sample 2. ----- Pure solid (equation [I]).

Tlze Purity of the Sanzples

T h e melting temperatures as a function of the fraction melted are given in
Table 11. From these results the calculated triple point of hydrogen peroxide
is 272.74" K. and the estimated impurity content 0.032 mole %.
TABLE I1
THEMELTING POINT OF Hz02
(0" C. = 273.16" K.)

% Melted T , I<.

Impz~rity:0.052 mole %.
Triple point: 272.74' K.

The degree of purity of the hydrogen peroxide used could also be estimated
from the heat capacity in the prenlelting region. T h e excess heat capacity was
calculated using (a) the phase diagram for the system H20-H202 (4) and
(b) a constant value for the heat of fusion (2987 cal./mole). The amount of
impurity was then so chosen that the derived heat capacity of the pure solid
 121 CANADIAN JOURNAL OF CHEMISTRY. 1,'OL. 32

was a linear function of the temperature. A calculated impurity of 0.038 mole

Ujo together with the expression for the heat capacity of the pure solid (plotted
in Fig. 3)
[I-] C, = 2.31 + 0.03967 T cal./mole deg.
suflice to represent the experimental results very closely between 220" and
271" I<. T h e good agreement between the estimates of impurity from the
melting temperatures and from the prelnelting heat capacities, as well a s the
shape of the heat capacity curve in the prelnelting region (2) provide definite
evidence that tlle impurity (water) does not form solicl solutions with hydrogen
peroxide. This coilfirms the results of two independent investigations of phase
equilibria in this binary system (4, 18).
DISCUSSION
T h e first important conclusion to be drawn from the above results is t h a t
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there are no transitions either of the first or the second order in solid hydrogen
peroxide, notwithstanding assertions to the contrary (18). This provides
further evidence that ordinary hydrogen peroxide contains no measurable
proportion of a tautomeric form, HZO-0, as has been suggested (29). Numer-
ous struct~iralst~idiesas well as recent measurelnents of the magnetic suscepti-
bility of the solid (21) and of the ionization potential of the molecule (25) may
be cited in support of this conclusion. On the other hand the possibility is not
ruled out that an ~lnstableisonler, such as proposed by Geib and Harteck (6),
could be formed under special conditions (low temperature reaction between
oxygen and atomic hydrogen, etc.). But this hypothetical isomer should not
be reversibly convertible into normal hydrogen peroxide.
T h e present results for the heat of fusion and the triple point of hydrogen
peroxide lie outside the limits of error assigned by Foley and Gig~16refor their
determinations (4, 5). Because the experimental method ~isedthis time was
nl~ichmore accurate there is no q~lestionthat the new values are to be pre-
ferred. T h e limitations of the freezing point method for measuring melting
points are well known (3). T h a t thermodynamic equilibri~irnwas not perfectly
realized in the determinations by the above authors was indicated by the
uncertainty of their calculated melting point a t zero impurity. fillore recent
measurements made with an improved type of apparatus (9) have yielded a
melting temperature of -0.43" C. for the pure compound (28) in agree-
ment with the present value after correction for the pressure effect (5)
(dt/dp = 0.007" a t m . 7 ) .
I t is perhaps worth emphasizing that the present calorimetric determin-
ation of impurities in hydrogen peroxide is the most precise reported so far.
T h e usual procedures based upoil chenlical ailalysis are not capable of a n
accuracy much greater than O.lyo. Because of this, previous workers have
often assumed erroneously that they had succeeded in preparing 100% pure
hydrogen peroxide.
The Entropy of Hydrogen Peroxide
T h e c o m p ~ ~ t a t i oofn the entropy of hydrogen peroxide from the thermal data
 is outlined in Table 111. The contribution of the solid between 12' I<. and the
triple point was deduced by integrating values of C,/T using Simpson's rule.
Up to 250' I<. the values of C, were talcen from Table I and thereafter fro111
equation [ I ] .
TABLE 111
THE ENTROPY OF H 2 0 2
--
I
I Cal./mole deg.
AS (0" t o 12' I<.) Debye extrapolatioi
AS (12" t o 272.74 " I<.) Solid
AS272.740(2987/272.74) Fusion
Entropy of the liquid a t 272.74O I<.
*AS (272.74" t o 298.16' I<.) Liquid
*AS?DB.,'
(12330/298.16) Vaporizatior~
**AScompressionR In (1.95/7GO)
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Correction for ideal gas

Entropy of the ideal gas a t
298.ltiUI<. and 1 atm. pressure

* Reference (IS). ** Reference (67).

An alternative calculation of the entropy of the liquid a t the triple point

was also made using only experimentally measured quantities. Up to 250' I<.
the procedure was as above. From 250' I(. to the point where melting was
complete, the total entropy was computed by means of the expression

where AQ,, is the energy supplied in the nth heat capacity lneasuremeilt and
T, is its mean temperature. From this was subtracted the increase in entropy
of the calorimeter vessel. The result of this calculatio~lwas within 0.01 cal./mole
deg. of that given in Table 111. Thus, to this degree of precision the entropy
of the liquid is independent of any assumption concerning the behavior of the
heat capacity of the pure solid in the premelting region.
The specific heat of the liquid was talcen as 21.35 cal./mole deg. and the
latent heat of vaporization as 12.33 kcal./mole a t 25' C. from the results of
recent redeterminations to be published soon ( 1 9 ) . For the entropy of com-
pression to one atmosphere the equilibrium vapor pressure of hydrogen
peroxide a t 25'C. (1.95 mm. Hg) was obtained by extrapolation of the
equation of Scatchard and co-workers (27). Finally, the Berthelot equation
of state with the approximate critical constants Tc = 459' C. ( l G ) , PC=
240 atm. ( 1 3 ) , was used to evaluate the small correction for gas imperfection.
The value thus obtained for the third law entropy a t 25' C. is significantly
higher than the entropy calculated previously by the statistical method
(54.18 cal./mole deg. ( 7 ) ) .Since the various structural and vibrational data of
the molecule are lcnown with fair accuracy, except those pertaining to the
internal rotational mode, it was obvious that the discrepancy was to be traced
 126 CANADZAN JOURNAL OF CHEIIIZSI'RY. 1'OL. 32

to the latter. On reviewing the statistical calculations, it was discovered that

an error had been made in selecting a value for n in the expression for the
rotational partition function (10)

Although the potential energy restricting free rotation about the 0-0 bond
exhibits two maxima, these are unequal and therefore distinguishable. Conse-
quentl)., n in equation [3] must be taken as 1 and not 2 as was chosen previ-
ously. After correcting this term, the statistical entropy is only 0.45 units
smaller than the third law entropy, and the two can be made equal by using
a barrier height of about 3.5 kcal./mole (instead of 5 kcal./mole as in the
earlier calculations (7)). Hitherto, values ranging from a few hundred
calories (17) up to 12 kcal./mole (12) have been proposed for the potential
barriers in hydrogen peroxide. The various thermodynamic functions for
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gaseous hydrogen peroxide have been recalculated up to 1500' I<. (Table IV),
TABLE IV
REVISEDVALUES OF THE THERMODYNAMIC FUNCTIONS FOR HYDROGEN PEROXIDE GAS
AT 1 ATM. PRESSURE

T.
" K.
- FO - fIoo ,
T
H 0 - Hoo ,
I So, cO, IT0 - Ho0,
cal./rnole deg. cal./mole
T~ deg. cal./mole deg. cal./mole deg. cal./mole deg.
I -

GOO 1 53.38 1 10.85 1 64.23 1 13.28 1 6511

the contribution of internal rotation being estimated. after the method of

Pitzer and Gwinn (24) with a barrier height V n = 3.5 kcal./mole and the
simple sinusoidal potential function
[4l V = +Vn(1 - cosno).
Because of this approxinlation there still remains some uncertainty in the
revised thermodynamic quantities, especially a t the higher temperatures.
The internal rotational inode may be treated differently, namely as a
double minimum oscillator such as the ammonia molecule. Then a satisfactory
approximation consists of talcing the energy levels for an equivalent single
minimum oscillator with each level being doubly degenerate (23). This is
tantamount to adding an R In 2 term to the entropy and free energy functions.
However, here again the calculated functions will be less accurate a t higher
 temperatures because then the molecules change gradually from pure oscil-
lation towards free internal rotation. I t turns out that the values of the entropy
calculated by the two methocls agree fairly well even a t 1500' I<.* but the
enthalpy and heat capacity functions are appreciably different. More exact
calculations of these various quantities must await further spectroscopic data
and an adequate theoretical treatment of the molecule.
ACKNOWLEDGMENT
The success of these experiments clepended to a large extent upon careful
fabrication of the calorimeter vessels. For this work the authors are indebted
to Messrs. A. Dubois, A. Lavergne, and F. C. Mason of the National liesearch
Laboratories. They also wish to thank Dr. A. Cholette of Lava1 University
for valuable assistance with the sealing of the vessels.

RBSUME
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L a capacitC calorilique du peroxyde dlhydrog&neA 1'Ctat solide a CtC mesurCe

entre 12' I<. et le point de fusion au moyen d'un calorim&treadiabatique. La
chaleur latente de fusion a Cgalement CtC dCterminCe et trouvbe &ale A
2987 f 3 cal./mole. Les deux Cchantillons d e peroxyde d'hydrogsne qui o n t
servi pour ces mesures Ctaient d'un haut degrk de puretC, soit 99.97 mole yo,
ainsi qu'il ressort des variations de la capacitk calorifique qui ont prCcCd6
fusion. D e ces mernes clonnCes on a dCduit que le point triple du peroxyde
dlhydrog&nese trouve B 272.74' I(.
La seule anomalie que l'on ait rernarquCe au cours des mesures fut l'absorp-
tion d'une faible quantitC de chaleur, 1.3 cal./mole, A 216.8" I<., le point
eutectique des solutions concentrhes du peroxyde d'hydrogsne. Cette observa-
tion conduit au meme rksultat que celui dCjA mention& pour la purete des
Cchantillons employks.
A partir de ces donnCes on peut calculer l'entropie calorimCtrique d u
peroxyde d'hydrogcne considCrC comine gaz parfait A 25" C. et B 1 atm. E n
cornparant cette valeur, (55.76 f 0.12 cal./mole deg.) avec celle que donne
la mCthode statistique il appert que la rotation interne des deux groupes OH
dans la lnolCcule est g&nCepar une Cnergie potentielle Cquivalente B un seuil
unique d'environ 3.5 Itcal./mole.

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