562 J. A.

DUIBMAN
AND W. F. GIAUQUE

Thermodynamics of the Lead Storage Cell. The Heat Capacity and

Entropy of Lead Dioxide from 15 to 318'K1

by J. A. Duisman and W. F. Giauque

Low Temperature Laboratory, Departments of Chemistry and Chemical Engineering,
University of California, Berkeley, California 94730 (Received July 17,1967)

The heat capacity of an electrolytic sample of lead dioxide has been measured from 15
to 318°K. The composition was PbO2.1.519 X 10-2Pb0.2.558 X 104H20. After
correction, the entropy of PbOz was found to be 17.16 gibbs/mol at 298.15'K. The en-
tropy change in the cell reaction, H2 +
PbO2 +
H2S04 (z M ) = PbSO4 2H20 (in x M +
H2S04), calculated from the third law of thermodynamics, is in excellent agreement with
dE/dT, as determined by Beck, Singh, and Wynne-Jones. This agreement supports the
use of third-law data on PbO2, Pb, PbS04, and H2S04 (z M ) to calculate the temperature
coefficient of the lead storage cell. The table of Giauque, Hornung, Kunzler, and Rubin,
on the thermodynamic properties of aqueous sulfuric acid, has been extended from 1 to
0.1 M . A table giving the change of voltage of the lead storage cell over the range 0-
60" and from 0.1 to 14 M H2S04 has been based on the third law of thermodynamics.
+ + +
For the reaction P b PbO2 2HzS04 (pure) = 2PbS04 2H20 (pure), AF" = -120,200
cal/mol and AH" = -121,160 cal/mol at 298.15"K. Numerous unsuccessful attempts
to prepare stoichiometric PbO2 are described.

For some time, one of the projects of this laboratory
has been directed toward the accumulation of third-law
entropy values on the reactants and products of the lead
storage cell. The present work on lead dioxide com-
pletes the necessary data. Previous researches are on
lead12aqueous sulfuric acidJ3and lead sulfates4
The possibility that any of these substances might
have "frozen in" entropy due to remnent disorder at
limiting low temperatures has always been considered
as negligible, with the exception of aqueous sulfuric
acid, where hydrogen bonds at least gave rise to sus-
picion. However, this possibility was thoroughly
eliminated by highly accurate third-law agreementa
among the phases HzS04, H2S04.H201 H2804' 2H20,
HzS04.3H20, HzS04.4H20, and H2S04.6.5HzO.
A very significant third-law comparison is available
by means of the cell reaction
H2 + PbOz + HzS04 (Z M ) =:
PbS04 + 2Hz0 (in z M H2S04) (1)
in which the PbOz, H2S04(aq),and PbS04 are largely
subject to the same conditions as those existing in the
lead storage cell. The principal investigations on cell 1,
which cover the range up to about 7 M H2S04,are those
of Hamer16 and Beck, Singh, and Wynne-JoneslBwho
review previous work. There is a t least a reasonable
expectation that the variable sulfuric acid concentration
does not alter the thermodynamic properties of the
solid phases in this cell. Thus, since the thermody-
namic properties of aqueous sulfuric acid are accurately
known, one of the tests of the above cell is to investigate
the effect of H2S04concentration on the cell potential,
and we are particularly interested in its effect on the
temperature coefficient. Beck, Singh, and Wynne-
Jones* apply this test to their data by means of the
Gibbs-Helmholz equation. They also calculate the
results of Hamer,5 who presents his temperature coeffi-
cient data only as smoothed equations. Hamer's
results show a total spread in the calculated heat of
reaction of the order of 400 cal/mol. Their own data
agree quite accurately with the known properties of
aqueous sulfuric acid. We have now found that the
temperature coefficients of the cell potential measured
by Beck, Singh, and Wynne-Jones,6 agree with those
derived from low-temperature heat capacity measure-
ments and the third law of thermodynamics, thus pro-
viding a very substantial basis for the use of the third
law in evaluating the temperature coefficient of the lead
storage cell. For this cell the generally accepted re-
action is
(1) This work was supported in part by National Science Founda-
tion Grant GP-6782.
(2) P.F. Meads, W. R. Forsythe, and W. F. Giauque, J. Am. Chem.
SOC.,63, 1902 (1941).
(3) W.F. Giauque, E. W. Hornung, J. E. Kunzler, and T. R. Rubin,
ibid., 82, 62 (1960).
(4)K. Gallagher, G. E. Brodale, and T. E. Hopkins, J . Phys. Chem.,
64, 687 (1960).
(6)W.J. Hamer, J . Am. Chem. Soc., 57, 9 (1936).
(6) W. H. Beck, K. P. Sin& and W. F. K. Wynne-Jones, Tram.
Faraday Soc., 55, 331 (1969).

The J O U Tof~Phyaical Chemistry

THERMODYNAMICS O F THE LEADSTORAGE CELL
Pb + PbO2 + l2HzSO4 (5 M HzS04) =
2PbS04 + 2Hz0 (in 2 M H2S04) (2)
Preparation and Analysis of PbOz Samples. This
research was started with the hope that some way could
be found to prepare a sample, close in composition to
stoichiometric I'bOz. We did not succeed. In every
case there was a deficiency of active oxygen. It was
also found that small amounts of water could not be re-
moved by drying in air, oxygen, or under vacuum with-
out serious loss of oxygen. This gave rise to the sus-
picion that water molecules may occupy some positions
to the exclusion of the second oxygen atom as an al-
ternative or additional explanation to simple oxygen
vacancies. Meyers' has also commented on his in-
ability to dry Pb02. An additional problem was that
many preparations were not crystalline in the macro-
scopic sense.
Experimenters, preparing PbOz for use in cells,
typically digest it with hot aqueous sulfuric acid with
the expectation that any PbO present would be con-
verted to PbS04. Since PbS04 is a product of the lead
cell, its presence is also typically ignored, which seems
reasonable. However, the typical ignoring of the
analysis of Pb02 samples for oxygen content by experi-
menters seems much less reasonable.
For analysis, samples were reduced by means of a
known excess of primary standard grade AszOa in 2 m
hydrochloric acid: method A, the excess As203 was
titrated with standardized potassium permanganate
solution from a weight buret; the color of the KMn04
served as the indicator; method B, the acid solution
was neutralized with sodium bicarbonate, and the lead
ions were complexed by the addition of ethylenediamine-
tetraacetic acid (EI4TA)s immediately before titration
with a standardized iodine solution to a starch end
point. The present attempts to obtain stoichiometric
PbOz may be divided into five categories: 1, chemical
preparations ; 2, elevated temperatures and high
oxygen pressures; 3, attempts at slow crystal growth in
liquids at 1 atm; 4, PbO2 mineral; and 5 , electrolytic
preparations.
Chemical Preparations. Most of these experiments
involved the oxidation of sodium plumbite in sodium
hydroxide solu.tion with chlorine, bromine, hydrogen
peroxide, and 37 M nitric acid. Also attempted was
the hydrolysis of a saturated solution of lead tetra-
acetate in glacial acetic acid. Three agents were used:
(1) water, (2) acetic acid containing 10 vol % water,
and (3) absolute ethanol.
One short experiment involved the hydrolysis of lead
tetrachloride with precooled water in hydrochloric acid
solution a t 0". The product was identical in ap-
pearance with the starting material (magnification =
SOX). No andysis was attempted. None of these
preparations produced a crystalline product.
Experiments at Elevated Temperatures and High
563
Oxygen Pressures. These experiments were performed
in a steel bomb. In order to protect the bomb from
corrosion, a nickel reaction vessel was made with a
Teflon check valve built into its top. The function of
this valve was to allow oxygen to enter the reaction
vessel when the bomb was pressurized but to prevent
sodium hydroxide solution from leaking out. In order
to release the pressure inside the reaction vessel when
the bomb was vented, a disk-type safety valve was also
built into the top of the reaction vessel.
The usual load for this apparatus was a slurry of
chemically prepared lead dioxide in 5 m sodium hy-
droxide. The bomb was pressurized with oxygen gas
to 2200 psig. Pressures as high as 8000 psig were ob-
tained a t the highest temperatures. Experiments were
made from 240 to 320" a t 20" intervals for periods
ranging from 5 days to 2 weeks. At the higher temper-
atures, small crystals were indeed formed, but analysis
by method B disclosed the active oxygen content to be
only 97-98% of the theoretical amount for PbOz.
Also attempted was the formation of crystalline lead
dioxide from powdered PbOz in a melt of 23.07%
LiN03, 53.85y0 KN03, and 23.07?70 NaNOs, by weight.
The melting point of this mixture was 145 f 5".
The experiment was performed a t an oxygen pressure
of 4000 psig and a temperature of 214 rJ, 5". Micro-
scopic examination (60X) of the lead dioxide indicated
no increase in particle size, and analysis by method B
showed no significant increase in active oxygen con-
tent, which was typically 98.5% of the theoretical for
PbOz, after the mixture was held a t these conditions for
7 days. This experiment was repeated with 2%
added Na202. The mixture was allowed to stand for 10
days a t 225 & 5" under a total pressure of 4000 psig.
Again no crystalline product was obtained.
Finally a mixture of 200 g each of PbO, KN03, and
KCIOz was placed in the nickel container and heated to
a temperature of 260" under 2000 psig of oxygen in the
bomb. A brown powder was formed which was identi-
cal in appearance with ordinary chemically prepared
PbOz. Its analysis gave an active oxygen content of
98y0 of the theoretical for PbOz.
Solubility Experiments Performed under a Pressure of
1 Atm. The idea behind these experiments was that if
a liquid could be found in which lead dioxide had a
reasonable solubility (say, mol/l.), this liquid
phase would provide a mechanism for the Pb02 in the
powdered form to convert itself to a macroscopic
crystalline form.
The starting material in all of these experiments was
commercially available lead peroxide, a brown powder.
The most thoroughly investigated solvent was con-
centrated nitric acid, and 1: 2, 1: 1, and 2: 1 dilu-
(7) R. G . Meyers, Anal. Chem., 20, 654 (1948).
(8) R. Pribil and J. Cihalik, Collect. Czech. Chem. Commun., 20, 562
(1955).
Volume 72, Number R February 1968
564
tions with water. A Pyrex flask containing nitric
acid mixed with the PbOz powder was placed in a ther-
mostat at 35" and mechanically agitated for periods up
to 6 months. The PbO2 was inspected under a micro-
scope before and after this treatment. No evidence of
any increase in particle size was observed. Analysis by
method B showed that the active oxygen content of the
material had actually decreased. Other experiments
a t 100" for shorter periods of time showed similar
results: before, 98.5-98.7y0; and after, 98.0-98.4%
of the theoretical active oxygen.
Other solvents were tested by the simple expedient of
placing them in a suitable container with some PbO2
powder and stirring them with a Teflon-clad magnet a t
ambient temperature for several weeks. niIicroscopic
examination indicated all these attempts to be failures.
Among the solvents tested in this manner were: per-
chloric acid (HC104~2H20),hydrofluoric acid (48%),
sodium hydroxide (various concentrations), formic
acid, acetic acid (various concentrations), and acetic
acid with 10% acetic anhydride.
Since lead dioxide has properties in common with
metals, liquid ammonia was also tested as a solvent,
merely by placing some powdered PbO2 in a dewar full
of solid ammonia, allowing the ammonia to melt, and
then slowly evaporating over a period of about 16 hr.
This experiment was performed in an explosion-proof
cubicle to minimize the danger of an explosion. None
occurred. Microscopic examination showed that the
lead dioxide did not benefit from this treatment.
In each case the mixture of Pb02plus test solvent was
poured onto a medium-porosity glass frit and washed
with water, 1 : l nitric acid (-18 N), and then more
water. It was then dried in air a t 150" for 2-4
hr.
Mineral Pb02. A sample of naturally occurring lead
dioxide (Plattnerite) was obtained through the courtesy
of Professor A. Pabst for this investigation. Its source
was a mine in Mullan, Idaho. Analysis of this black
crystalline material by method A showed it to contain
-92% of the theoretical amount of active oxygen for
PbO2.
Electrolytic Experiments. Various materials were
tested for use as anodes. Among them were graphite,
Hastelloy C (Union Carbide Stellite Co., Kokomo,
Ind.), nickel, stainless steel, and platinum. Platinum
was found to be the most suitable, and most of the ex-
periments utilized a rotating cylinder 6 cm in diameter
and 9 cm tall, made of 0.013 in. thick platinum sheet.
Various electrolytes were tested, the most notable of
which was a nearly saturated solution of lead per-
chlorate in perchloric acid-water eutectic.9 The elec-
trolysis was perforped a t anode current densities of
1 and 2 mA/cm2, using a platinum anode and a graphite
cathode a t temperatures near -50". Analysis of the
product by method A gave 96.4% of the theoretical
active oxygen for PbO2, with no significant difference
The Journal of Physical Chemistry
AND W. F.GIAUQUE
J. A. DUISMAN
between the materials prepared at the different current
densities.
Also electrolyzed were solutions of lead perchlorate in
water, lead acetate in water and in glacial acetic acid,
lead nitrate in water with various nitric acid concen-
trations, and solutions of sodium plumbite a t various
concentrations of plumbite and sodium hydroxide. A
lead cylinder served as a cathode in these experiments.
The effect of acid concentration was investigated
using lead nitrate-nitric acid solutions in water by
adding neutral lead nitrate solution to the electrolysis
solution at such a rate to maintain the concentration of
nitric acid at a fixed value. Experiments covered the
range from nearly neutral solutions to a hydrogen ion
concentration of 2 M. At the highest acidities, the
active oxygen content of the product declined, but
there was no clear evidence that a solution of 0.1 M
"03 was superior to one with 1.0 M "03.
It was suspected that NO2- ions, formed at the
cathode by reduction of Nos- ions, might be having an
adverse effect on the oxygen content of the sample.
This possibility was investigated and eliminated through
the use of a solution of lead nitrate and copper nitrate
as electrolyte, since Collat and Linganel" have shown
that electrolytic reduction of nitrate ions proceeds all
the way to NH4+in the presence of Cu2+. No signifi-
cant change in the active oxygen content of the samples
produced was observed.
In the case of the lead nitrate solutions, the effect of
rotating the anode a t different speeds was also investi-
gated. It was observed that a t high speeds the porosity
of the sample decreased slightly. The products, pre-
pared at speeds higher than 100 rpm, all had essentially
the same active oxygen content.
The effect of current density was also investigated.
Using 1 m lead nitrate solution as the electrolyte,
several current densities ranging from 1.2 to 46.3 d/
cm2 were tested. Again, no significant effect on the
active oxygen content was observed. However, the
samples prepared a t low current densities had a more
crystalline appearance. All of the samples contained
about 98.5% of the theoretical active oxygen for
PbO2.
Since the search for a method of preparing stoichio-
metric Pb02 had produced nothing better, it was de-
cided that the heat capacity of the electrolytic material
would be measured and corrections applied to the exper-
imental heat capacity for the effect of the impurities.
Preparation of the Calorimetric Sample. The calori-
metric sample was prepared by electrolysis of 1 M
aqueous lead nitrate. The rotating cylindrical plati-
num anode was 6 cm in 0.d. and 9 cm long. It was con-
centric with a cylindrical lead cathode. The electrodes
(9) A. Seidell and W. F. Linke, "Solubilities of Inorganio Com-
pounds," 4th ed, John Wiley and Sons, Inc., New York, N. Y., 1968.
(10) J. W. Collat and J, J, Lingane, J . Am. Chem. Soc., 7 6 , 4214
(1964).
 OF THE LEADSTORAGE
THERMODYNAMICS CELL
were separated by a vessel of sintered aluminum oxide,
which was friction-fitted internally with four radial
stationary Teflon paddles to facilitate stirring within
the anode chamber. The base of the platinum cylinder
was fitted with a Teflon plug, so that only the outer
surface served as an anode. As recommended by
Palmaer,ll the platinum cylinder was rotated a t 450 f
20 rpm.
The lead nitrate solution was prepared from Baker
Analyzed Pb(NO&. The anode current density was
stabilized a t about 2.3 X A/cm2. This current
density was chosen because, according to Singh'sla
experience, onky p-PbOz (tetragonal) was formed by
electrolysis of neutral solutions of lead nitrate with a
current density of 1-2 mA/cm2.
During the electrolysis, new solution was added to the
anode chamber to maintain a steady flow rate of 1 cmS/
min through the porous aluminum oxide diaphragm.
This was done to prevent a decrease in lead ion con-
centration and to keep the hydrogen ion concentration
from rising.
The product was a dense gray layer with a definite
metallic luster. The conglomerate was broken with a
mortar and pestle to pass a 10 mesh/in. screen, placed
in a beaker with 2 1. of distilled water, and stirred vigor-
ously with a motor-driven stirrer for 12 hr. This
washing procedure was repeated five times.
The sample was then treated with 2 1. of ~ 2 M4"OS
for 3.5 hr in an attempt to dissolve any oxide lower
than PbOz. The water-washing procedure was then
repeated four times. It was dried in air a t 125" for
2 hr. Two batches were prepared in this manner.
Analysis of the Sample. The two batches were
analyzed separately for active oxygen by treating
samples of approximately 2 g with an excess of an
accurately known weight of primary standard grade
arsenious oxide, in the presence of hydrochloric acid,
under 1 atm of nitrogen. The reaction flask was fitted
with a reflux condenser to prevent evaporation of
arsenic trichloride. The solution was then neutralized
with sodium bicarbonate and the lead ions complexed
with EDTA.* The excess arsenite was titrated from a
weight buret to a starch end point with standard iodine
solution. In each case, a measured correction was
applied for the effect of the starch and EDTA on the
end point. The results were as follows: batch I
(weight per cent of active 0),6.5880; 6.5826; 6.586070;
and 6.5855 f 0.0023, av wt yo; and batch I1 (weight
per cent of active 0), 6.5753; 6.5867; 6.5746%; and
6.5789 0.0052, av w t %. A 306.74-g sample of
batch I was then thoroughly mixed with 185.92 g of
batch 11, giving a weighted average of 6.5830 f
0.0034% for the active oxygen content.
The combined sample wm then analyzed for lead by
converting approximately 2-g samples to lead sulfate.
The results are given in Table I.
A test was made for nitrate in the original sample,
565
Table I : Lead -Content of Combined Sample
% Pb % PbO
86.537 93.219
86.547 93.230
86.316" 92.981"
86.550 93.233
AV 86.545 k 0.008% 93.227 k 0.009%
a The third test was given no weight in computing the average.
using diphenylamine and concentrated sulfuric acid
under the conditions suggested by Treadwell and Hall13
after dissolving it with acetic acid and hydrogen perox-
ide. The nitrate content of the sample was less than
0.005%, which was the limit of detection.
The sample was analyzed for water by heating 55-g
portions in a stainless steel tube with a diameter of
about 2 cm; the water was swept through the tube into
a weighed trap containing phosphorous pentoxide by a
stream of dry nitrogen gas. A blank run was performed
immediately before each determination, while the
stainless steel tube was heated to a dull red heat by
means of a gas-air torch. No water was evolved.
Nitrogen gas was passed over the sample a t a rate of
3 l./min. As %I check, the experiment was repeated on
the residue left in the stainless steel tube; no further
water was evolved. Three samples were analyzed in
this manner. The results for the water content of the
combined sample are 0.1902, 0.1893, and 0.1894%.
The average water content is 0.1896 f 0.0004%. As a
check, one can add: Pb as PbO, 93.227 f: 0.009;
0, 6.583 f 0.0034; and HzO, 0.190 f 0.0004'%.
The sum of these is 100.000 f 0.013%. All atomic
weights used are based on the carbon-12 s~a1e.I~
Although we had enough confidence in Singh's'2
experience to complete heat capacity experiments on
the above sample, we decided that an X-ray examina-
tion should be made to complete the record. This was
done through the courtesy of Professor D. H. Templeton
with the disagreeable result that the sample was found
to contain some of the orthorhombic form (a-PbOz)
discovered by Zoslavskii, Kondrashov, and Tolkachev.lS
On the basis of rough intensity measurements, the
investigated material may be estimated to have con-
tained about 25% a-PbOz.
In this situation, it was decided to prepare a new
sample with a repetition of the heat capacity measure-
ments. This sample was made in the manner used for
(11) W.Palmaer, Medd. Nohelinst., 5 , 1 (1919).
(12) K. P. Singh, personal communication.
(13) F. P. Treadwell and W. T. Hall, "Analytical Chemistry,"
John Wiley and Sons, Inc., New York, N. Y., 1937,p 418.
(14) A. E. Cameron and E. Wichers, J. Am. Chem. SOC.,84, 4175
(1962).
(16) A. I. Zoslavskii, Y. D. Kondrashov, and S. S. Tolkachev,
Dokl. Akad. Nauk SSSR, 7 5 , 559 (1950).
Volume 78, Number W FehruaTy 1968
566
making the calorimetric sample with the following
exceptions: (1) the current density used was 1.07 X
loF3A cm-2 and (2) to maintain the lead and hy-
drogen ion concentrations, lead carbonate was added
to the bath instead of the previously used flow system.
Unfortunately the new sample contained about the
same fraction of a-PbO2 (orthorhombic) as the previous
one.
Several additional samples were then prepared:
I, electrolysis of 1 M Pb(NOa)z with H + maintained a t
0.5 M ; the current density was held a t 6 mA/cm2; and
X-ray examination showed about the same fraction of
a-PbOz as before; 11, the same procedure as method I
was used, except that the bath was maintained at 60"
during electrolysis; the a-Pb02 impurity persisted in
about the same percentage; 111, aqueous 0.6 M PbAcz
was electrolyzed, with a current density of about 2 mA/
cm2; X-ray examination showed an unacceptable,
nearly amorphous substance in which about 1% of
crystalline a-Pb02 was present; and IV, a commercial
sample (method of preparation unknown, but pre-
sumably chemical) was washed with -18 M " 0 3
followed by distilled water; after drying in an oven a t
125", X-ray analysis showed a crystalline product with
about 5% of the orthorhombic form.
There was no reason to believe that any of the above
materials would be appreciably superior to that already
measured. Unfortunately we were unaware of the
work of White, Dachille, and RoyJL6 which showed that
a-PbO2 slowly converts to P-Pb02 at 100". Singh12has
estimated that a-PbOz gives a potential 10 mV higher
than P-Pb02 in reaction 1. There is probably little
difference in their heat capacities. However, it is
difficult to see how definitive answers can be obtained
until stoichiometrically pure, macroscopically crystal-
line samples become available for each of these crystal-
line forms, in the considerable amounts needed for
accurate calorimetry.
Another difficult problem is concerned with the dis-
covery of Clark, Schieltz, and Quirke," that PbsOs also
has essentially the same tetragonal lattice as PbOz.
The presence of this material, which is essentially
oxygen deficient PbOz, could explain the difficulty in
attaining 100% active oxygen in our numerous prepa-
rations and the difficulty in removing the PbO by
treatment with acid.
Davidson18 also carried out an X-ray analysis of
Pb508 and showed an excellent photograph of crystals of
this material prepared for his investigation.
In the case of the sample prepared for our calori-
metric measurements, we have simply assumed that
the deficiency of active oxygen corresponds to a PbO
content, and since the fractional amount is small, there
is unlikely to be appreciable error due to a heat capacity
correction based on the assumption of simple additivity.
Heat Capacity Measurements. The low-temperature
heat-capacity apparatus was similar to one described by
The Journal of Physical Chemistry
J. A. DUISMANAND W. F. GIAUQUE
Giauque and Egan,l8 and the particular copper calo-
rimeter has been described by Kemp and Giauque.20
The more recent record of the calorimeter has been
summarized by Bartky and Giauque.21 The original
He thermometer temperature scale was corrected to 0"
= 273.15"K.
Laboratory standard copper-constantan thermo-
couple no. 105 was used as a temperature reference
before and after every heat input. High-precision
thermometry utilized a gold resistance thermometer
heater wound on the exterior surface. The standard
thermocouple was checked against the triple (13.95"K)
and boiling (20.39"K) points of normal hydrogen, and
the triple (63.14"K) and boiling (77.32"K) points of
nitrogen. It was 0.09" low a t 13.95"K, 0.07" low
at 20.37"K, and 0.01" low at both the triple and boil-
ing points of nitrogen. Appropriate corrections were
made.
The heat capacity of 1 mol of sample is given in
Table 11. The mole was defined as 1 mol of PbO2 +
+
0.01519 mol of PbO 0.02558 mol of H20,with a molec-
ular weight of 243.040. The temperature rise of the in-
dividual runs is not given; however, the runs were con-
tinuous and the AT'S may be inferred approximately
from the separations of their average temperatures.
Corrections for the amount of PbO and H 2 0 present
were made from the data of King22for red lead monox-
ide and the data of Giauque and Stout2afor ice, with
an extrapolation above 0", since, as expected, the heat
capacity measurements indicated that fusion of the
entrapped H2O did not occur. The corrected values
are given in Table I1 as the molal heat capacity of PbOz.
The smoothed thermodynamic properties of PbO2 are
given in Table 111. Although the measurements
terminated near 308"K, they have been extrapolated
to 330"K, since cell data involving PbO2 extend through
this range. The extrapolation below 15°K was made
by plotting CJT2 us. T , which leads to the result
CP(O-15"K) = 7.0 X 10-5T3 gibbs/mol
S(O-15°K) = 7.0 X 10-5Ta/3 gibbs/mol
S(15"K) = 0.079 gibbs/mol
The heat capacity data of Millar24 on PbO2 average
about 7% higher than the present results. As will be
(16) W. B.White, F. Dachille, and R. Roy, J . Am. Ceram. Soc., 44,
170 (1961).
(17) G. L.Clark, N. C. Schieltz, and T. T. Quirke, J. Am. Chem. Soc.,
59, 2305 (1937).
(18) H.R. Davidson, Am. Mineralogist, 26, 18 (1941).
(19)W. F. Giauque and C. J . Egan, J. Chem. Phys., 5, 45 (1937).
(20) J. D. Kemp and W. F. Giauque, J. Am. Chem. SOC., 59, 79
(1937).
(21) I. R.Bartky and W. F . Giauque, {bid., 81, 4169 (1959).
(22) E.G. King, ibid., 80, 2400 (1958).
(23) W. F. Giauque and J. W. Stout, ibid., 58, 1144 (1936).
(24) R. W. Millar, (bid., 51, 207 (1929).
 OF THE LEADSTORAGE
THERMODYNAMICS CELL 567

Table 11: Heat Capacity of Lead Dioxide Samplea~b~o Table I11 : Thermodynamic Properties of Lead Dioxide5gb
T,
QK
CP
Sample
CP
PbOv T,
"K SO
(HO
HOe)/T
- -(PO
H0d/T
-
CPO
Series 2
0.157d 15 0.238 0.079 0.059 0.020
13.87 0.168d
0.262 20 0.539 0.184 0.136 0.048
15.56 0.276
0.377 25 0.982 0.351 0.260 0.091
17.65 0.397
0.500 30 1.407 0.567 0.414 0.153
19.44 0.524
35 1.848 0.817 0.588 0.229
21.48 0.696 0.666
0.842 40 2 339 1.095 0.775 0.320
23 -49 0.878 I

25.33 0.987d 0. 945d 45 2.827 1.364 0.949 0.415

27.45 1.231 1.182 50 3.284 1.685 1.160 0.525
30.23 1.421 55 3.765 2.021 1.375 0.646
1.478
33.63 1.799 1.732 60 4.231 2 369 1.603 0.766
37.47 2.137 2.059 70 5.067 3.085 2.039 1.046
41.64 2.590 2.501 80 5.812 3.812 2.466 1.346
45.73 3.001 2.903 90 6.488 4.536 2.875 1.661
50.31 3.410 3.302 100 7.141 5.254 3.270 1.984
55.30 4.061d 3.943d 110 7.762 5.964 3.650 2.314
60.29 4.378 4.251 120 8.334 6.664 4.017 2.647
65.90 4.879 4.741 130 8.869 7.352 4.370 2.982
72.03 5.226 140 9.416 8.029 4.710 3.319
5.375
78.43 5.864 5.704 150 9.908 8.696 5.041 3.655
84.96 6.330 6.159 160 10.35 9.350 5.359 3.991
91.52 6.783 6.602 170 10.79 9,991 5.666 4.325
98.41 7 229
I 7.037 180 11.19 10.619 5.962 4.657
190 11.58 11.234 6.247 4.987
Series 1 200 11.94 11.838 6.523 5.315
71.42 5.311 5.172 210 12.27 12.428 6.789 5.639
78.38 5.904 5.744 220 12.63 13.008 7.047 5.961
85.54 6.363 6.191 230 12.93 13.577 7.297 6.280
91.65 6.793 6.611 240 13.21 14.135 7 * 539 6.596
98.05 7.208 7.016 250 13.47 14.679 7.771 6.908
104.53 7.573 7.371 260 13.74 15,213 7.996 7.217
111.21 8.029 7.818 270 14.01 15.736 8.213 7.523
117.37 8.403 8.183 273.15 14.08 15.899 8.280 7.619
126.05 8.897 8.665 280 14.23 16.250 8.424 7.826
133.06 9.269 9.028 290 14.45 16.753 8.628 8.125
140.13 9.641 9.392 298.15 14.58 17.156 8.790 8.366
147.27 10.040 9.782 300 14.60 17.246 8325 8.421
154.33 10.358 10.092 310 14.73 17.727 9.014 8.713
161.14 10.683 10.408 320 (14.85) (18.196) (9.194) (9,002)
168.03 11.000 10.718 330 (14.97) (18.655) (9.367) (9.288)
179.42 11.448 11,153
186.39 11.755 11.452 (I All units are gibbs per mole. 1 defined cal = 4.1840 abs
193.56 11.999 11.688 J; 1 gibbs = 1 defined cal/defined OK.

200.65 12.222 11.903

207.14 12.546 12.220
214.44 12.764 12.430 evident from the third-law comparison to be given
221.92 13.043 12.701
229.63 13.394 13.044
below, his entropy value of 18.27 gibbs/mol a t 25", in
237.09 13.495 13.137 comparison with the present result of 17.16 gibbs/moI,
244.42 13.697 13.332 would lead to a discrepancy of about 1 gibbs/mol.
251.58 13.884 13.517 The Reaction of Hydrogen, Aqueous Sulfuric Acid,
258.61 14.096 13.716 and Lead Dioxide. Beck, Singh, and Wynne-Joness
265.76 14.351 13.964
272.61 14.405 14.012
measured the emf of the cell for the reaction
279.12
286.67
14.572
14.805
14,173
14.398 H2 + PbO2 + HzS04 (ZM ) =
295.65
304.34
14.918 14.502 PbSO4 + 2H20 (in z M HzS04)
15.227 14.803
5 Sample: Pb0~~0.01519Pb0.0.02558H20;molecular weight a t 5, 10, 20, 25, 35, 45, and 55", with ten sulfuric acid
243.040; and C, is in gibbs per mole. b482.087-g sample in concentrations which ranged from 0.1000 to 7.199 M .
the calorimeter. 1 defined cal = 4.1840 abs J; 1 gibbs = Their measurements were made with great care and
1 defined cal/defi.ned OK. d These measurements were given showed excellent reproducibility. They have cal-
no weight when the smooth curve was drawn.
culated the temperature coefficient of the emf a t 25"

Volume 72, Number 2 Felrruary 1968

568 J. A. DUISMAN
AND W. F. GIAQUUE

Table IV : Entropy Change from the Third Law and from the Their results have been multiplied by the factor
Temperature Coefficient of Cell Reaction I%* 1.00111 to convert them to gibbs/mol (Le,, defined
cal/deg mol).
Dis- The extension of the tablea of the partial molal
--dE -A#, crepanoy
dT -AS, third cell - properties of aqueous sulfuric acid is given as Table V.
Heso4 10' 0011 law 3rd law The values for 1 M are taken from ref 3.
0.1000 0.4320 19.93 20.00 -0.07 The entropy change, based on the third law of
0.1996 0.3967 18.30 18.21 f0.09 thermodynamics, for reaction 1, is given at even values
0.2917 0.3721 17.16 16.82 f0.34 of concentration in Table VI and is shown as the curve
0.4717 0.3290 15.18 15.15 f0.03
1.129 0.2570 11.85 11.93 -0.08
in Figure 1, along with the experimental points of
2.217 0.2122 9.79 9.65 +0.14 Beck, Singh, and Wynne-Jones." The agreement is
3.900 0.2104 9.70 9.46 $0.24 qcellent and gives strong support to the use of closely
4.973 0.2314 10.67 10.29 +0.38 related third-law data in deriving the temperature
6.095 0.2417 11.15 11.16 -0.01 coefficient of the lead storage cell.
7.199 0.2512 11.59 11.81 -0.22
The entropy change, as calculated from the tempera-
a Cell data of Beck, Singh, and Wynne-Jones.' The H &
% ture coefficients given by Hamer,6 is also included in
concentration is given in molar units; dE/dT is given in absolute Figure 1. It is evident that there is a serious error.
volts per degree; AS is given in gibbs per mole of PbOz (1 gibbs =
1 defined cal/defined deg). The results of Hamer6 have received owing to
the fact that the variations with sulfuric acid con-
centration are similar to those found in the cell for
for the various concentrations, and we have reproduced
the values given in their Table 3 in our Table IV, which
Hz + HgzSOc + 2Hg (4)
also gives the entropy change from the relation AS = by Harned and HamerS80 However, Brackett, Horn-
nF(dE/dT), where n F = 2 X 23062.4 = 46125 cal/ ung, and Hopkinssl have shown that the results of
abs V equiv. The entropy change for reaction 1 is
given by H z t PbO2rHZSO4(iMI* PbSO*+ ZHeO (in aMtizS041

AS = So(PbS04) + 2.%(H20in x M HzS04) - 19

Curve based on third l o w
x Beck, Singh, and Wynne-Jones
(dUdT call-1959)

#'El - S'(Pb0z) - sz(HzS04 in x M HzS04) (3)

I§''(P~SO~)~ = 35.509 gibbs/mol
at 298.15'K
S(PbO2) = 17.156 gibbs/mol
a t 298.15'K and
S(Hz)26= 31.211 gibbs/mol
at 298.15' K.
Sl(HzO in x M HzS04)and Sz(HzS04 in x M HzS04)
are given, a t 298.15'K, for concentrations above 1 M
in Table I of ref 3. In order to cover the range 8.01 I 1 I I I I 1 I
I 1
of the experimental data for reaction 1, we have ex- 0 1 2 3 4 5 6 7 8 9
M HZSO4
tended Table I of Giauque, Hornung, Kunzler, and
Rubina on the thermodynamic properties of aqueous Figure 1. Entropy change during reduction
sulfuric acid to 0.1 M . This has been done by utilizing of PbOa by HZin z M HzSO4.
the activity and osmotic coefficients of Stokesz6to give
the free energy change. Since the reference states for (25) "JANAF Thermochemical Tables," Thermal Research Labore
the above table3 are pure %?So4and HzO, we are con- tory, Dow Chemical Co., Midland, Mich., March 1961.
cerned only with the relative rather than the absolute (26) R. H. Stokes, Trans. Faraday Soc., 44, 295 (1948).
values of the activity coefficients of Stokes, because (27) T. F. Young, private communication; W. L. Groenier, Thesis,
University of Chicago, Chicago, Ill., 1936; Y. C. Wu, Thesis, Uni-
they appear only as ratios in extending the table. versity of Chicago, Chicago, Ill., 1957.
The relative partial molal enthalpies of sulfuric acid (28) M. Randall and M. D. Taylor, J . Phys. Chem., 45, 959 (1941).
and water, needed to give their partial molal entropies, (29)H. S. Harned and B. B. Owen, "The Physical Chemistry of
are taken from the work of Young, Groenier, and WU.~' Electrolytic Solutions," Reinhold Publishing Corp., New York,
N. Y., 1968,p 577.
The partial molal heat capacities of HzS04 and HzO in (30) H. 9. Harned and W. J. Hamer, J . Am. Chem. Soc., 57, 27
their solutions have been given by Randall and Taylor.28 (1935).

The Journal of Physical Chemistry

THERMODYNAMICS
OF THE LEAD CELL
STORAGE 569

~~~~ ~

Table V : Relative Partial Molal Free Energies, Enthalpies, Entropies, and Heat Capacities
for Aqueous Sulfuric Acid from 0.1 to 1 M at 298.15"K4

555.06 0.1 2.15 18 656 1.08 17 742 16.714 40.567 17.994 10.15
227.53 0.2 4.23 17 850 1.13 17 525 16.720 38.591 17.989 11.87
185.02 0.3 6.35 17 369 2.04 17 428 16.724 37 303
I 17.984 13.10
138.77 0.4 8.50 17 020 2.42 17 369 16.730 36.330 17.976 13.86
111.01 0.5 10.71 16 744 2.80 17 322 16.737 35.562 17.966 15.49
92.51 0.6 12.96 16 514 3.19 17 282 16.743 34.925 17.955 16.64
79.29 0.7 15.28 16 314 3.62 17 245 16.749 34.378 17.942 17.84
69.38 0.8 17.71 16 131 4.09 17 210 16.756 33.882 17.928 18.96
61.67 0.9 20.24 15 903 4.63 17 174 16.762 33.439 17.913 19.86
55.506 (l.O)b (22.84) (15 811) (5.29) (17 138) (16.769) (33.050) (17.896) (21.03j
0 A = moles of H20per mole of HzS04; M = moles of HzSOaper 1000 g of HzO; 1, H20; 2, HzS04; F and L are in defined calories

per mole; S and C', are in gibbs per mole (1 gibbs = 1 defined cal/defined deg). Values for 1M are taken from ref 3.

Table VI: The Entropy Changes a t 298.15"K, from the Third Law of Thermodynamics,
and the Change in Heat Capacity, for Reactions 1 and Zntb

- AB(l), As(2), E(2)So

A M 298.15'K Acp(1) 298.15OK Acp(2) 298.15"K

555.06 0.1 20.00 29.03 -9.36 44.03 1.7971

277.53 0.2 18.01 27.30 -5.39 40.57 1.8322
185.02 0.3 16.71 26.06 -2.81 38.10 1.8531
132.77 0.4 15.73 25.29 -0.85 36.58 1,8683
111.01 0.5 14.95 23.64 +0.70 33.30 1.8804
92.51 0.6 14.30 22.47 1.98 30.97 1.8905
79.29 0.7 13.74 21.24 3.09 28.55 1.8993
69.38 0.8 13.23 20.09 4.10 26.27 1.9073
61.67 0.9 12.77 19.16 4.99 24.44 1.9147
55.506 1.0 12.37 17.96 5.79 22.07 1.9213
50.0 1.110 12.00 16.94 6.52 20.07 1.9283
40.0 1.388 11.17 15.30 8.14 16.86 1.9441
30.0 1.850 10.13 13.82 10.15 13.98 1.9669
25.0 2.220 9.65 13.31 11.08 13.01 1.9833
20.0 2.775 9.30 13.02 11.76 12.44 2.0065
17.5 3.172 9.22 12.96 11.91 12.34 2.0223
15.0 3.700 9.35 13.63 11.66 13.59 2.0425
12.0 4.626 10.01 15.73 10.43 26.18 2.0760
10.0 5 551
I 10.74 24.53 9.09 33.87 2.1076
9.0 6.167 11* 19 25.38 8.26 35.42 2.1278
8.0 6.938 11.67 25.60 7.40 35.82 2.1559
7.0 7.929 12.12 24.96 6.59 34.68 2.1812
6.5 8.539 12.29 23.87 6.29 32.76 2.1981
6.0 9.291 12.43 21.57 6.04 28.71 2.2169
5.5 10.092 12.52 18.44 5.89 23.26 2.2382
5.0 11.101 12.57 15.32 5.80 17.88 2.2633
4.5 12.335 12.60 12.88 5.75 13.73 2.2897
4.0 13.877 12.64 10.79 5.69 10.21 2.3210
A = moles of HzO per mole of HzSO4; M = moles of HzSO~per 1000 g of HzO; A S and AC, are in gibbs per mole (1 gibbs =
1 defined cal/defined deg); E is in absolute volts. Data for computing A S and AC, are taken from ref 2, 3, 4, and 25 and Tables
+ + +
I1 6nd 111. (1) HZ PbOz HzS04 (in HzS04.AHzO) = PbSO4 2Hz0 (in HzSO4.AHzO); (2) Pb PbOz 2H~S04(in HzS04. + +
+
AHzO) = 2PbSO4 2 H ~ (in -
0 HBOd.AHz0). 0 Calculated from AF"tss.1~= 120,200 cal/mol. (See eq 10.)

Harned and Hamer on this cell also show third-law
deviations which are comparable in magnitude to the
discrepancies shown in Figure 1. The actual obser-
vations of Harned and Hamer30 and of Hamers have
never been published, so it is particularly to
attempt to trace the source of the discrepancy; how-
ever, we believe that their equations should be given no
weight with respect to the variation of the properties
of aqueous sulfuric acid with concentration or tempera-
ture.
(31) T. E. Bracket$, E. W. Hornung, and T. E. Hopkins, J . Am.
Chem. sot., 82,4155 (ieso).

Volume 78, Number 8 February 1968

570
Table VI also includes values of AC, for reaction 1.
With the assistance of A8298.15 from the third law
and the measured ACp, we may write
AFT - AF298.15 = - ~ F ( E T- E298.16) (5)
AFT - AF298.16 = (ACp - ASz98,lj)(T - 298.15) -
AC,T In (T/298.15) (6)
It should be noted that the effect of AC, nearly cancels
in the two terms on the right side of eq 6 for moderate
values of ( T - 298.15). Thus variation of AC, with
temperature should have little effect over the range of
existing experimental data. It is due to this fact that
Beck, Singh, and Wynne-Jones were able to derive
accurate values of ASZgs.ljby considering derivatives
over a total range of some 50".
Equation 6, with values of AS and AC, from Table
VI, should accurately represent the change of emf with
temperature for reaction 1, over all concentrations of
aqueous HzS04, excepting those limiting situations
where the solubility of PbS04 could interfere with the
properties of the solution.
The Thermodynamic Properties of the Fundamental
Reaction in the Lead Storage Cell. I n Table VI, we
have also included values of AS2g8.1j and AC,, over a
range of concentration, for the reaction
Pb + PbOz + 2HzS04 (Z M ) =
2PbS04 + 2H20 (in z M H2S0J
which has been generally accepted as applicable to the
lead storage cell.
I n Figure 2, we have shown the third-law value of
ASze8.150Ii: for reaction 2 as a curve. The experimental
values of Vosburgh and Craigla2the 1933 values of
Vinal and Craig,33and those of Hamerj6 all of which
are taken from the dE/dT summary of Craig and
are shown as points.
The temperature coefficient values of Vosburgh and
Craig are in good agreement with the third law of
thermodynamics. They were given only to 0.01 mV/
deg or about 0.5 gibbs/mol. Vosburgh and Craig
studied reaction 2 by indirect means which separated
the two most troublesome substances, namely, the
PbO2 and Pb, in contact with sulfuric acid. The cell
reactions were
Pb(two-phase amalgam) + in which all of the reactants and products are taken as
Hg2S04 = PbSOd + 2Hg (7)
2Hg + PbOz + 2HZS04 M ) = (Z
PbSOl + Hg2S04 + 2Hz0 (in z M HzS04) (8)
Pb = Pb(two-phase amalgam) (9)
Reaction 9 and its temperature coefficient had been
investigated by Gerke.35
The emf of reaction 7 was found to be E298.16 =
The Journal of Physical Chmistry
J. A. DUISMAN
AND W. F. GIAUQUE
IS
10
- 5
<
Y)
n
e
- 5
P O h t s from d U d T summory of Cralg and Vinal.
-10
0 1 2 3 4 5 6 7 8
M HpS04
Figure 2. Entropy change in lead storage cell. Experimental
data of several observers are taken from a summary by
Craig and Vinal (NBS Research Paper 1294, 1940).
0.96466 int V, and that of reaction 9 as E298.16 = 0.0057
int V. The emf of reaction 8 is included in the sum of
the three reactions given in Table VI1 which should
correspond to reaction 2 in the lead storage cell. It has
been convenient to retain all of the results as inter-
national volts and convert them to calories per mole by
means of the factor 23,070 defined cal/int V equiv. Es-
sentially all of the thermodynamic properties of aqueous
sulfuric acid have been reinvestigated since the work of
Vinal and Craig. Much of that reinvestigation was
stimulated by the fact that attempts in this laboratory
to make third-law comparisons on the sulfuric acid
hydrates disclosed the inadequacy of the early work on
this substance. The data of Vinal and Craiga3 on
directly measured lead cells are also given in Table VII,
but it is evident that, although the average value is
practically identical with that of Vosburgh and Craig,
it can be given no weight in selecting a final value for
AF", which corresponds to the reaction
Pb + PbO2 + 2HzS04 = 2PbS04 + 2820 (10)
AF'298.15 = - 120,200 cal/mol
pure.
Taking the entropies of lead, pure sulfuric acid, and
pure water as
(32) W.C. Vosburgh and D. N. Craig, J . Am. Chem. SOC.,51, 2009
(1929).
(33) G. W. Vinal and D. N. Craig, J . Res. Natl. BUT.Std., 14, 449
(1936).
(34) D.N. Craig and G. W. Vinal, ibid., 24, 476 (1940).
(36) R. H.Gerke, Chem. Rev.,1, 382 (1926); J. Am. Chem. SOC.,44,
1684 (1922).
THERMODYNAMICSOF THE LEADSTORAGE
CELL 57 1

i3°(Pb)2 = 15.514 gibbs/mol 46125E(z M &Sod) =

a t 298.15"K -AFo + 2(F1" - PI) - 2(F2" - Fz) (11)
So(HzS04)a= 37.501 qibbs/mol where E is in absolute volts. Values of (F1" Fl) -
and (F2"- &) for water and sulfuric acid in their solu-
a t 298.15OK and
tions are given in Table I of ref 3, supplemented by
S0(H20)3= 16.710 gibbs/mol Table V above. Values of for reaction 2
have been calculated from eq 11 and were entered in
at 298.15"K and combining with the other entropy
Table VI above. Equation 6, giving values of (ET -
values given a,bove, the entropy change in reaction 10 is
E298.15) applies equally to reactions 1 and 2, except of
found to be
course that the appropriate values of As298.16 and ACp
AS'298.16 = -3.23 gibbs/mol for each reaction must be used. The necessary values
for reactions 1 and 2 were included in Table VI. They
have been used to compute the variation of the emf of
and a rounded value of the heat of reaction may be the lead storage cell reaction with temperature from
taken as 273.15 to 333.15"K, over a range of concentration
extending from 0.1 M HzS04 to HzS04.4H20, although
AH"288.15 = -121,160 cal/mol the concentration HzS04.8H20 (6.938 M ) represents
Values for the AH in the lead storage cell may be about the practical upper limit of the lead cell. The
obtained for any concentration of HzS04 in this cell calculated values have been given in Table VIII. The
by combining the above value of AHo with data from values of concentration above 1 M correspond to simple
Table I in ref 3 as extended by Table V. The emf values of A in H2S04.AH20 as shown in Table VI.
of the lead storage cell at 298.15"K is given by eq 11. It has ordinarily been considered that the tempera-
ture coefficient of the reaction in the lead storage cell
was more uncertain than the potential itself. The use
of the third law has reversed this situation, in that we
Table VII: The Free-Energy Change in the Reaction consider the temperature coefficient to be considerably
Pb +
Pb0z +
2HzS04 = 2PbSOa 2HzO'nb + more reliable than the voltage. Thus the separation
- AF030s.1s, of the data into values of (E298.16 - ET)in Table VI11
[HzSOr,1 E, defined
M int V ca1/ m o1 has been done with the expectation that this portion
of the data will have a considerable degree of perma-
Data of Vosburgh and Craig82
0.05355 1 ,76596 *.. nence. While we do not know, there is much reason to
0.1000 1.79616 120 183 question whether any preparation of PbO2 has ever
0.1035 1 .79906 120 082c qualified as a macroscopic crystal. Thus the measured
0.2579 1.84506 120 168 cell potential may be higher than that of truly macro-
0.5154 1 .88096 120 175 scopic PbO2. There is not much reason to believe that
1.036 1 .92296 120 193
1.065 1.92536 120 221 the entropy of microscopic PbOz would exceed that of
1.964 1.97166 120 209 macroscopic PbO2 by more than a very small amount,
2.206 1 ,98246 120 220 although the free energy of the small particles may be
3.499 2 03416d
I 120 196 considerably greater.
Av 120 196 f 16 The best experimental evidence on this subject has
Data of Vinal and Craigss been found in the data on Mg0.36 In that case, ex-
0.321 1.855 120 138 ceedingly fine MgO was prepared by vacuum dehydra-
0.486 1.876 120 096 tion of Mg(OH)z a t temperatures low enough to avoid
0.655 1.892 120 073 sintering of the MgO. The enthalpy of the colloidal
0.806 1.905 120 101 material exceeded that of the macroscopic crystals of
1.760 1.962 120 193
MgO by about 900 cal/mol, whereas the entropy in-
2.773 2.005 120 167
3.902 2.050 120 236 crease was only of the order of about 0.2 gibbs/mol
5.206 2.098 120 318 near 500°K. This corresponds with what would be
6.092 2.128 120 353 expected. While the surface material on small par-
6.713 2.148 120 368 ticles is subject to somewhat smaller bond restraints, a
Av 120 204 5 7 9 property which can lead to measurable heat capacity
(Fz0- -
&) and (FI" PI) are taken from ref 3 and Table percentage effects a t very low temperatures, it fails to
III.
FI)H*O
AFo = - ~ F E z M 2(Fz0
in z M E~so,,.
- - O~ -
F ~ ) Z M H ~ S 2(Fio
Excluded from average. d The final digit
+ add much to the heat capacity or entropy a t higher
6 comes only from reaction 6, which was measured more ac-
temperatures. Thus the energy required to break a
curately than reactions 7 and 8.
(36) W. F. Giauque, J . Am. Chem. Soc., 71, 3192 (1949).

Volume 76,Number d February 1968

572 J. A. DUISMAN
AND W. F. GIAUQUE

B
3

Y
..

The Journal of Physical Chemistry

 IN THE THORIUM
HEATSOF IMM:ERSION OXIDE-WATERSYSTEM 573

large crystal into smaller ones is largely an increment of
enthalpy.
For the above reasons, it seems quite possible that
someone may find a method of producing a more
macroscopic form of PbOz, giving a lower and more
fundamental potential than the one commonly found
for the lead storage cell. However, there would appear
to be doubtful practical advantage in trying to accom-
plish this. If ithe typical lead cell is able to store a small
additional amount of energy, owing to the higher free
energy of microscopic lead dioxide, there is no obvious
reason to discourage any such serendipity. In this
sense the values for Ezes.legiven in Table VI may
also have considerable permanence.
Acknowledgment. We thank R. H. Lamoreaux and
P. R. Siemens for assisting with the low-temperature
measurements on PbOz, D. H. Templeton for numerous
X-ray diffraction patterns and their analysis, and A.
Pabst for supplying a mineral sample of PbOz for
analysis.

Heats of Immersion in the Thorium Oxide-Water System, 111. Variation

with Specific Surface Area and Outgassing Temperature112

by E. L. Fuller, Jr., H. F. Holmes, C. H. Secoy, and J. E. Stuckey

Reactor chemistry Division, Oak Ridge National LabOTdOTy, Oak Ridge, Tennessee 97860
(Received July 17, 1067)

The heats of immersion of thorium oxide samples in water show that there are three modes
of interaction of water with the surface and further elucidate the temperature realms of
stability for these surface species. Considerable evidence is shown that high-temperature
calcination produces material that is nearly devoid of the high-energy surface hetero-
geneities present in the original high surface area material. These conclusions are based
on data for 25-500' outgassing of thoria samples with specific surface areas ranging from
1 to 35 m2/g. Samples with high specific surface areas liberated a portion of their
immersional heat via two kinetically controlled processes, in addition to the instantaneous
portion.

Introduction oxalate. The physical properties of this series are given

In the continuing investigation of the nature of the
interaction of water with the surface of thorium dioxide,
a second series of heats of immersion has been measured
to be compared to previous ~ o r k . ~The t ~ variation of
heats of immersion with respect to specific surface area
and outgassing; temperature is recognized as a useful
tool for evaluation of the water-oxide i n t e r a ~ t i o n . ~ - ~
We hope that this work may help to elucidate the
water-thorium oxide interaction, as well as oxide-water
systems in general.
Experimental Section
The equipment and techniques employed for this
study have been described in detail in an earlier re-
port. Following the technique used earlier, samples
of thoria were calcined from an initial batch to produce
samples of lesser specific surface area. Both series
were prepared by a 650' decomposition of thorium
in Table I. Table I1 gives the impurity analyses of
the initial 650' calcined material. The loss-of-ignition
(LOI) data are questionable, owing to the strong contri-
butions of environmental conditions.
Results
The low-fired, high surface area samples F, G, and H,
(1) Reaearch sponsored by the U. S. Atomic Energy Commission
under contract with the Union Carbide Corporation.
(2) Presented in part a t the 163rd National Meeting of the American
Chemical Society, Miami Beach, Fla., April 1967.
(3) H. F. Holmes and C. H. Secoy, J . Phys. Chem., 69, 161 (1966).
(4) H. F. Holmes, E. L. Fuller, Jr., and C. H. Secoy, {bid., 70, 436
(1966).
(6) J. A. G. Taylor, J. A. Hockey, and B. A. Pethica, Proc. Brit.
Ceram. SOC.,5 , 133 (1966).
(6) J. A. G. Taylor and J. A. Hockey, J . Phys. Chem., 70, 2169
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(7) A. C. Zettlemoyer, R. D. Iyengar, and P. Scheidt, J . Colloid
Interface Sci., 22, 172 (1966).

Volume 76, Number 6 February 1968