Escolar Documentos
Profissional Documentos
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DUIBMAN
AND W. F. GIAUQUE
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 known, one of the tests of the above cell is to investigate
has been directed toward the accumulation of third-law the effect of H2S04concentration on the cell potential,
entropy values on the reactants and products of the lead and we are particularly interested in its effect on the
storage cell. The present work on lead dioxide com- temperature coefficient. Beck, Singh, and Wynne-
pletes the necessary data. Previous researches are on Jones* apply this test to their data by means of the
lead12aqueous sulfuric acidJ3and lead sulfates4 Gibbs-Helmholz equation. They also calculate the
The possibility that any of these substances might results of Hamer,5 who presents his temperature coeffi-
have "frozen in" entropy due to remnent disorder at cient data only as smoothed equations. Hamer's
limiting low temperatures has always been considered results show a total spread in the calculated heat of
as negligible, with the exception of aqueous sulfuric reaction of the order of 400 cal/mol. Their own data
acid, where hydrogen bonds at least gave rise to sus- agree quite accurately with the known properties of
picion. However, this possibility was thoroughly aqueous sulfuric acid. We have now found that the
eliminated by highly accurate third-law agreementa temperature coefficients of the cell potential measured
among the phases HzS04, H2S04.H201 H2804' 2H20, by Beck, Singh, and Wynne-Jones,6 agree with those
HzS04.3H20, HzS04.4H20, and H2S04.6.5HzO. derived from low-temperature heat capacity measure-
A very significant third-law comparison is available ments and the third law of thermodynamics, thus pro-
by means of the cell reaction viding a very substantial basis for the use of the third
H2 + PbOz + HzS04 (Z M ) =:
law in evaluating the temperature coefficient of the lead
storage cell. For this cell the generally accepted re-
PbS04 + 2Hz0 (in z M H2S04) (1) action is
in which the PbOz, H2S04(aq),and PbS04 are largely
subject to the same conditions as those existing in the (1) This work was supported in part by National Science Founda-
lead storage cell. The principal investigations on cell 1, tion Grant GP-6782.
which cover the range up to about 7 M H2S04,are those (2) P.F. Meads, W. R. Forsythe, and W. F. Giauque, J. Am. Chem.
SOC.,63, 1902 (1941).
of Hamer16 and Beck, Singh, and Wynne-JoneslBwho (3) W.F. Giauque, E. W. Hornung, J. E. Kunzler, and T. R. Rubin,
review previous work. There is a t least a reasonable ibid., 82, 62 (1960).
expectation that the variable sulfuric acid concentration (4)K. Gallagher, G. E. Brodale, and T. E. Hopkins, J . Phys. Chem.,
64, 687 (1960).
does not alter the thermodynamic properties of the
(6)W.J. Hamer, J . Am. Chem. Soc., 57, 9 (1936).
solid phases in this cell. Thus, since the thermody- (6) W. H. Beck, K. P. Sin& and W. F. K. Wynne-Jones, Tram.
namic properties of aqueous sulfuric acid are accurately Faraday Soc., 55, 331 (1969).
tions with water. A Pyrex flask containing nitric between the materials prepared at the different current
acid mixed with the PbOz powder was placed in a ther- densities.
mostat at 35" and mechanically agitated for periods up Also electrolyzed were solutions of lead perchlorate in
to 6 months. The PbO2 was inspected under a micro- water, lead acetate in water and in glacial acetic acid,
scope before and after this treatment. No evidence of lead nitrate in water with various nitric acid concen-
any increase in particle size was observed. Analysis by trations, and solutions of sodium plumbite a t various
method B showed that the active oxygen content of the concentrations of plumbite and sodium hydroxide. A
material had actually decreased. Other experiments lead cylinder served as a cathode in these experiments.
a t 100" for shorter periods of time showed similar The effect of acid concentration was investigated
results: before, 98.5-98.7y0; and after, 98.0-98.4% using lead nitrate-nitric acid solutions in water by
of the theoretical active oxygen. adding neutral lead nitrate solution to the electrolysis
Other solvents were tested by the simple expedient of solution at such a rate to maintain the concentration of
placing them in a suitable container with some PbO2 nitric acid at a fixed value. Experiments covered the
powder and stirring them with a Teflon-clad magnet a t range from nearly neutral solutions to a hydrogen ion
ambient temperature for several weeks. niIicroscopic concentration of 2 M. At the highest acidities, the
examination indicated all these attempts to be failures. active oxygen content of the product declined, but
Among the solvents tested in this manner were: per- there was no clear evidence that a solution of 0.1 M
chloric acid (HC104~2H20),hydrofluoric acid (48%), "03 was superior to one with 1.0 M "03.
sodium hydroxide (various concentrations), formic It was suspected that NO2- ions, formed at the
acid, acetic acid (various concentrations), and acetic cathode by reduction of Nos- ions, might be having an
acid with 10% acetic anhydride. adverse effect on the oxygen content of the sample.
Since lead dioxide has properties in common with This possibility was investigated and eliminated through
metals, liquid ammonia was also tested as a solvent, the use of a solution of lead nitrate and copper nitrate
merely by placing some powdered PbO2 in a dewar full as electrolyte, since Collat and Linganel" have shown
of solid ammonia, allowing the ammonia to melt, and that electrolytic reduction of nitrate ions proceeds all
then slowly evaporating over a period of about 16 hr. the way to NH4+in the presence of Cu2+. No signifi-
This experiment was performed in an explosion-proof cant change in the active oxygen content of the samples
cubicle to minimize the danger of an explosion. None produced was observed.
occurred. Microscopic examination showed that the In the case of the lead nitrate solutions, the effect of
lead dioxide did not benefit from this treatment. rotating the anode a t different speeds was also investi-
In each case the mixture of Pb02plus test solvent was gated. It was observed that a t high speeds the porosity
poured onto a medium-porosity glass frit and washed of the sample decreased slightly. The products, pre-
with water, 1 : l nitric acid (-18 N), and then more pared at speeds higher than 100 rpm, all had essentially
water. It was then dried in air a t 150" for 2-4 the same active oxygen content.
hr. The effect of current density was also investigated.
Mineral Pb02. A sample of naturally occurring lead Using 1 m lead nitrate solution as the electrolyte,
dioxide (Plattnerite) was obtained through the courtesy several current densities ranging from 1.2 to 46.3 d/
of Professor A. Pabst for this investigation. Its source cm2 were tested. Again, no significant effect on the
was a mine in Mullan, Idaho. Analysis of this black active oxygen content was observed. However, the
crystalline material by method A showed it to contain samples prepared a t low current densities had a more
-92% of the theoretical amount of active oxygen for crystalline appearance. All of the samples contained
PbO2. about 98.5% of the theoretical active oxygen for
Electrolytic Experiments. Various materials were PbO2.
tested for use as anodes. Among them were graphite, Since the search for a method of preparing stoichio-
Hastelloy C (Union Carbide Stellite Co., Kokomo, metric Pb02 had produced nothing better, it was de-
Ind.), nickel, stainless steel, and platinum. Platinum cided that the heat capacity of the electrolytic material
was found to be the most suitable, and most of the ex- would be measured and corrections applied to the exper-
periments utilized a rotating cylinder 6 cm in diameter imental heat capacity for the effect of the impurities.
and 9 cm tall, made of 0.013 in. thick platinum sheet. Preparation of the Calorimetric Sample. The calori-
Various electrolytes were tested, the most notable of metric sample was prepared by electrolysis of 1 M
which was a nearly saturated solution of lead per- aqueous lead nitrate. The rotating cylindrical plati-
chlorate in perchloric acid-water eutectic.9 The elec- num anode was 6 cm in 0.d. and 9 cm long. It was con-
trolysis was perforped a t anode current densities of centric with a cylindrical lead cathode. The electrodes
1 and 2 mA/cm2, using a platinum anode and a graphite
cathode a t temperatures near -50". Analysis of the (9) A. Seidell and W. F. Linke, "Solubilities of Inorganio Com-
pounds," 4th ed, John Wiley and Sons, Inc., New York, N. Y., 1968.
product by method A gave 96.4% of the theoretical (10) J. W. Collat and J, J, Lingane, J . Am. Chem. Soc., 7 6 , 4214
active oxygen for PbO2, with no significant difference (1964).
were separated by a vessel of sintered aluminum oxide, Table I : Lead -Content of Combined Sample
which was friction-fitted internally with four radial
stationary Teflon paddles to facilitate stirring within % Pb % PbO
the anode chamber. The base of the platinum cylinder
86.537 93.219
was fitted with a Teflon plug, so that only the outer 86.547 93.230
surface served as an anode. As recommended by 86.316" 92.981"
Palmaer,ll the platinum cylinder was rotated a t 450 f 86.550 93.233
20 rpm. AV 86.545 k 0.008% 93.227 k 0.009%
The lead nitrate solution was prepared from Baker a The third test was given no weight in computing the average.
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 using diphenylamine and concentrated sulfuric acid
experience, onky p-PbOz (tetragonal) was formed by under the conditions suggested by Treadwell and Hall13
electrolysis of neutral solutions of lead nitrate with a after dissolving it with acetic acid and hydrogen perox-
current density of 1-2 mA/cm2. ide. The nitrate content of the sample was less than
During the electrolysis, new solution was added to the 0.005%, which was the limit of detection.
anode chamber to maintain a steady flow rate of 1 cmS/ The sample was analyzed for water by heating 55-g
min through the porous aluminum oxide diaphragm. portions in a stainless steel tube with a diameter of
This was done to prevent a decrease in lead ion con- about 2 cm; the water was swept through the tube into
centration and to keep the hydrogen ion concentration a weighed trap containing phosphorous pentoxide by a
from rising. stream of dry nitrogen gas. A blank run was performed
The product was a dense gray layer with a definite immediately before each determination, while the
metallic luster. The conglomerate was broken with a stainless steel tube was heated to a dull red heat by
mortar and pestle to pass a 10 mesh/in. screen, placed means of a gas-air torch. No water was evolved.
in a beaker with 2 1. of distilled water, and stirred vigor- Nitrogen gas was passed over the sample a t a rate of
ously with a motor-driven stirrer for 12 hr. This 3 l./min. As %I check, the experiment was repeated on
washing procedure was repeated five times. the residue left in the stainless steel tube; no further
The sample was then treated with 2 1. of ~ 2 M4"OS water was evolved. Three samples were analyzed in
for 3.5 hr in an attempt to dissolve any oxide lower this manner. The results for the water content of the
than PbOz. The water-washing procedure was then combined sample are 0.1902, 0.1893, and 0.1894%.
repeated four times. It was dried in air a t 125" for The average water content is 0.1896 f 0.0004%. As a
2 hr. Two batches were prepared in this manner. check, one can add: Pb as PbO, 93.227 f: 0.009;
Analysis of the Sample. The two batches were 0, 6.583 f 0.0034; and HzO, 0.190 f 0.0004'%.
analyzed separately for active oxygen by treating The sum of these is 100.000 f 0.013%. All atomic
samples of approximately 2 g with an excess of an weights used are based on the carbon-12 s~a1e.I~
accurately known weight of primary standard grade Although we had enough confidence in Singh's'2
arsenious oxide, in the presence of hydrochloric acid, experience to complete heat capacity experiments on
under 1 atm of nitrogen. The reaction flask was fitted the above sample, we decided that an X-ray examina-
with a reflux condenser to prevent evaporation of tion should be made to complete the record. This was
arsenic trichloride. The solution was then neutralized done through the courtesy of Professor D. H. Templeton
with sodium bicarbonate and the lead ions complexed with the disagreeable result that the sample was found
with EDTA.* The excess arsenite was titrated from a to contain some of the orthorhombic form (a-PbOz)
weight buret to a starch end point with standard iodine discovered by Zoslavskii, Kondrashov, and Tolkachev.lS
solution. In each case, a measured correction was On the basis of rough intensity measurements, the
applied for the effect of the starch and EDTA on the investigated material may be estimated to have con-
end point. The results were as follows: batch I tained about 25% a-PbOz.
(weight per cent of active 0),6.5880; 6.5826; 6.586070; In this situation, it was decided to prepare a new
and 6.5855 f 0.0023, av wt yo; and batch I1 (weight sample with a repetition of the heat capacity measure-
per cent of active 0), 6.5753; 6.5867; 6.5746%; and ments. This sample was made in the manner used for
6.5789 0.0052, av w t %. A 306.74-g sample of
batch I was then thoroughly mixed with 185.92 g of (11) W.Palmaer, Medd. Nohelinst., 5 , 1 (1919).
batch 11, giving a weighted average of 6.5830 f (12) K. P. Singh, personal communication.
0.0034% for the active oxygen content. (13) F. P. Treadwell and W. T. Hall, "Analytical Chemistry,"
The combined sample wm then analyzed for lead by John Wiley and Sons, Inc., New York, N. Y., 1937,p 418.
converting approximately 2-g samples to lead sulfate. (14) A. E. Cameron and E. Wichers, J. Am. Chem. SOC.,84, 4175
(1962).
The results are given in Table I. (16) A. I. Zoslavskii, Y. D. Kondrashov, and S. S. Tolkachev,
A test was made for nitrate in the original sample, Dokl. Akad. Nauk SSSR, 7 5 , 559 (1950).
making the calorimetric sample with the following Giauque and Egan,l8 and the particular copper calo-
exceptions: (1) the current density used was 1.07 X rimeter has been described by Kemp and Giauque.20
loF3A cm-2 and (2) to maintain the lead and hy- The more recent record of the calorimeter has been
drogen ion concentrations, lead carbonate was added summarized by Bartky and Giauque.21 The original
to the bath instead of the previously used flow system. He thermometer temperature scale was corrected to 0"
Unfortunately the new sample contained about the = 273.15"K.
same fraction of a-PbO2 (orthorhombic) as the previous Laboratory standard copper-constantan thermo-
one. couple no. 105 was used as a temperature reference
Several additional samples were then prepared: before and after every heat input. High-precision
I, electrolysis of 1 M Pb(NOa)z with H + maintained a t thermometry utilized a gold resistance thermometer
0.5 M ; the current density was held a t 6 mA/cm2; and heater wound on the exterior surface. The standard
X-ray examination showed about the same fraction of thermocouple was checked against the triple (13.95"K)
a-PbOz as before; 11, the same procedure as method I and boiling (20.39"K) points of normal hydrogen, and
was used, except that the bath was maintained at 60" the triple (63.14"K) and boiling (77.32"K) points of
during electrolysis; the a-Pb02 impurity persisted in nitrogen. It was 0.09" low a t 13.95"K, 0.07" low
about the same percentage; 111, aqueous 0.6 M PbAcz at 20.37"K, and 0.01" low at both the triple and boil-
was electrolyzed, with a current density of about 2 mA/ ing points of nitrogen. Appropriate corrections were
cm2; X-ray examination showed an unacceptable, made.
nearly amorphous substance in which about 1% of The heat capacity of 1 mol of sample is given in
crystalline a-Pb02 was present; and IV, a commercial Table 11. The mole was defined as 1 mol of PbO2 +
sample (method of preparation unknown, but pre- +
0.01519 mol of PbO 0.02558 mol of H20,with a molec-
sumably chemical) was washed with -18 M " 0 3 ular weight of 243.040. The temperature rise of the in-
followed by distilled water; after drying in an oven a t dividual runs is not given; however, the runs were con-
125", X-ray analysis showed a crystalline product with tinuous and the AT'S may be inferred approximately
about 5% of the orthorhombic form. from the separations of their average temperatures.
There was no reason to believe that any of the above Corrections for the amount of PbO and H 2 0 present
materials would be appreciably superior to that already were made from the data of King22for red lead monox-
measured. Unfortunately we were unaware of the ide and the data of Giauque and Stout2afor ice, with
work of White, Dachille, and RoyJL6 which showed that an extrapolation above 0", since, as expected, the heat
a-PbO2 slowly converts to P-Pb02 at 100". Singh12has capacity measurements indicated that fusion of the
estimated that a-PbOz gives a potential 10 mV higher entrapped H2O did not occur. The corrected values
than P-Pb02 in reaction 1. There is probably little are given in Table I1 as the molal heat capacity of PbOz.
difference in their heat capacities. However, it is The smoothed thermodynamic properties of PbO2 are
difficult to see how definitive answers can be obtained given in Table 111. Although the measurements
until stoichiometrically pure, macroscopically crystal- terminated near 308"K, they have been extrapolated
line samples become available for each of these crystal- to 330"K, since cell data involving PbO2 extend through
line forms, in the considerable amounts needed for this range. The extrapolation below 15°K was made
accurate calorimetry. by plotting CJT2 us. T , which leads to the result
Another difficult problem is concerned with the dis-
CP(O-15"K) = 7.0 X 10-5T3 gibbs/mol
covery of Clark, Schieltz, and Quirke," that PbsOs also
has essentially the same tetragonal lattice as PbOz. S(O-15°K) = 7.0 X 10-5Ta/3 gibbs/mol
The presence of this material, which is essentially
S(15"K) = 0.079 gibbs/mol
oxygen deficient PbOz, could explain the difficulty in
attaining 100% active oxygen in our numerous prepa- The heat capacity data of Millar24 on PbO2 average
rations and the difficulty in removing the PbO by about 7% higher than the present results. As will be
treatment with acid.
Davidson18 also carried out an X-ray analysis of
(16) W. B.White, F. Dachille, and R. Roy, J . Am. Ceram. Soc., 44,
Pb508 and showed an excellent photograph of crystals of 170 (1961).
this material prepared for his investigation. (17) G. L.Clark, N. C. Schieltz, and T. T. Quirke, J. Am. Chem. Soc.,
In the case of the sample prepared for our calori- 59, 2305 (1937).
metric measurements, we have simply assumed that (18) H.R. Davidson, Am. Mineralogist, 26, 18 (1941).
the deficiency of active oxygen corresponds to a PbO (19)W. F. Giauque and C. J . Egan, J. Chem. Phys., 5, 45 (1937).
content, and since the fractional amount is small, there (20) J. D. Kemp and W. F. Giauque, J. Am. Chem. SOC., 59, 79
(1937).
is unlikely to be appreciable error due to a heat capacity (21) I. R.Bartky and W. F . Giauque, {bid., 81, 4169 (1959).
correction based on the assumption of simple additivity. (22) E.G. King, ibid., 80, 2400 (1958).
Heat Capacity Measurements. The low-temperature (23) W. F. Giauque and J. W. Stout, ibid., 58, 1144 (1936).
heat-capacity apparatus was similar to one described by (24) R. W. Millar, (bid., 51, 207 (1929).
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
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
~~~~ ~
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
Harned and Hamer on this cell also show third-law ever, we believe that their equations should be given no
deviations which are comparable in magnitude to the weight with respect to the variation of the properties
discrepancies shown in Figure 1. The actual obser- of aqueous sulfuric acid with concentration or tempera-
vations of Harned and Hamer30 and of Hamers have ture.
never been published, so it is particularly to
(31) T. E. Bracket$, E. W. Hornung, and T. E. Hopkins, J . Am.
attempt to trace the source of the discrepancy; how- Chem. sot., 82,4155 (ieso).
B
3
Y
..
large crystal into smaller ones is largely an increment of energy of microscopic lead dioxide, there is no obvious
enthalpy. reason to discourage any such serendipity. In this
For the above reasons, it seems quite possible that sense the values for Ezes.legiven in Table VI may
someone may find a method of producing a more also have considerable permanence.
macroscopic form of PbOz, giving a lower and more Acknowledgment. We thank R. H. Lamoreaux and
fundamental potential than the one commonly found P. R. Siemens for assisting with the low-temperature
for the lead storage cell. However, there would appear measurements on PbOz, D. H. Templeton for numerous
to be doubtful practical advantage in trying to accom- X-ray diffraction patterns and their analysis, and A.
plish this. If ithe typical lead cell is able to store a small Pabst for supplying a mineral sample of PbOz for
additional amount of energy, owing to the higher free analysis.
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.