STUDIES ON THE THERMODYNAMICS AND CONDUCTANCES OF

MOLTEN SALTS AND THEIR MIXTURES

PART 111. DENSITIES, MOLAR VOLUMES, VISCOSITIES, AND SURFACE TENSIONS
O F MOLTEN LITHIUM CHLORATE, WITH SMALL ADDITIONS OF WATER, AND
OTHER SUBSTANCES

AND D. F. WILLIAMS
A. N. CAIVIPBELL
Chemistry Departwzent, University of illanitoba, TVinnipeg, Manitoba
Received March 10, 1964
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ABSTRACT
The density (2.088 g cc-I) a t 131.8 "C and viscosity (0.35 P a t 131.8 "C) and their tem-
perature dependence, of molten lithium chlorate, have been determined. Similar results have
been obtained for lithiu~nchlorate melts containing small quantities of water. The surface
tension and its temperature dependence have been determined for lithium chlorate a n d for
several l i t h i ~ ~chlorate
~n -water and lithium chlorate - lithiu~nnitrate nlixtures. From these
measurements the surface heat has been calculated.
T h e r e s ~ ~ l tfor
s pure lithiu~nchlorate indicate that the melt is comples, this complesity
probably caused by association of some kind. This is especially evident just above the ~nelting
point, since there the temperat~lrechange in properties is greatest.
Addition of water to the lithium chlorate melt causes the melt properties, especially the
viscosity, to alter considerably. These changes are in part caused by a breakdown of the
structural entities in the melt.

In this paper we report our experimental data on the density, viscosity, and surface
tension of lithiulll chlorate (a single-salt melt). As well we report sonle results for mixtures
in which a second component (water or lithium nitrate) was added to lithium chlorate,
to assess the sensitivity of these physical properties to the addition of polar molecular
species, as well as inorganic salts, as foreign species. I t is allowable to discuss these effects
in terllls of structure, although such a discussion cannot be considered as proving any
hypothetical structure.
EXPERIMESTAL
T h e theoretical implications a n d the experimental methods used in determini~lgdensiiy and viscosity
have been described in Parts I and I1 of this series (1, 2). I t should be mentioned, however, that since water
was added in these experiments, i t was essential t h a t the lithium chlorate be originally completely anhydrous.
Accordingly, the residual water, if any, in our preparation was determined by gas chromatography. X
precision Chro~nofracVP-7 unit was calibrated for water detection by injection of samples of 0.01 ml ethyl
alcohol containing known alno~untsof water. T h e lower limit of detection was found t o be 1 part water in
500 parts alcohol by volume. The clried, powdered lithium chloraie was weighed, mixed with dry sand, and
heated strongly. Under the catalytic action of the sand, the lithium chlorate deco~iiposedrapidly, evolving
oxygen together with any ~iioisturei t contained. T h e gases were trapped in a liquid nitrogen trap. A test of
the residue showed that decomposition was complete. T h e trapped gases were allorved to warln LIP slowly
to 0 "C a n d a ~ueasuredquantity of ethyl alcohol then added. This solution was allowed to warm LIPto roo111
temperature a n d a portion passed through the chromatograph. T h c result showed that the lithium chlorate
contained less than 0.006% water by weight. T h e specificconductivity a t 131.8 "C of a sample of this lithium
chlorate was found to be 0.1150+0.0002 Q-' and, for all subsequent preparations, this conductance was used
as the criterion of the absence of moisture in the specinlen. T h e co~lductivitywater used had a specific
conductance of 1.5 X 10-7 Q-l.
The method of capillary rise was used for the determination of surface te~lsion.T h e apparatus is shown
in Fig. 1. T h e inner tube was a precision-bore capillary tube, internal diameter 0 . 5 ~ t 0 . 0 0 1mm. >In estension
5 c n wide
~ a t the foot of the outer tube made possible a satisfactory reading of the level of the lower meniscus,
always a matter of uncertainty in the capillary rise method. T h e capillary rise was measured by means of a
micro-cathetonleter, which could be read to 0.01 mm.
The cell was loaded in a dry box with a weighed amount of lithium chlorate, sufficient in amount t o cover,
when molten, the maximum area of the bottom extension. lieighed amounts of additional substances were
Canadian Journal of Chemistry. Volume 42 (1961)

1778
 CAMPBELL AND WILLIAMS: STUDIES ON MOLTEN SALTS. 111
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.-
t - CAPILLARY TUBING
i.d. 0 . 5 rnrn

FIG.I. Surface tension apparatus.

added when necessary. After transference of the apparatus to the thermostat and attainment of temperature
equilibrium, the liquid was caused t o rise and fall in the capillary by suitably altering the esternal pressure
through the vacuum cocks. After each rise and fall, the capillary rise was measured. T o test the apparatus,
the surface tension of conductance water was determined in it, a t 25 "C, and found t o be reproducible to
f0.5 dyn cm-l.
RESULTS
Density and illolar Volume
The density of pure molten lithiii~nchlorate was determined a t teinperatures ranging
between ca. 130" to 150°, as well as those of mixtures containing 0.046, 0.130, and 0.223
mole fraction water. There is a ~naximumpossible error of 8.0 X l o p 4g cc-I in these
measuren~ents.The results are shown in Table I.
The density in each case was found to be linear with respect to temperature, the
coefficient of expansion decreasing with increasing water content. The molar volumes,
together with the coefficients of expansion, calculated from the relation V , = Vo(1 at) +
are shown in Table 11.
Equations of forills which have been sho\vn experimentally to represent the density-
teillperature relationship for fused salts have been calculated b17 a least squares fit of the
experinlental results of Table I , using a computer. These equations are given in Table 111.
Viscosity
The viscosities of pure inolten lithium chlorate, and of nlixtures containing 0.079,
0.197, and 0.251 mole fraction water, were determined a t temperatures between 130" and
180". The results are given in Table IV.
Both for pure lithium chlorate and the three mixtures with water, a linear relation
exists between log 7 and 1 / T . The activation energies of viscous flow mere obtained from
these graphs, as AE,,, = 4.576 X slope. The values of the coilstants are given in Table V.
The Arrhenius equations used to represent the viscosity-temperature relations were
determined by least squares fit, and they are also included in Table V.
 ChK.4DIAN JOURNAL O F CIIBMISTRY. VOL. 42, 1064

TABLE I
Density and molar volume of pure lithium chlorate and lithium chlorate - water
mixtures

Density Molar volurne

t ("c) ( g CC-1 (cc mole-')
Pure lithium chlorate

2. oson
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Lithium chlorate -water m i x t ~ ~ r e

Xole fraction water 0.046

AIole fraction nVatcr0.130

LlIole fraction water 0.223

TABLE I1
Molar volume ancl coefficient of expansion of
lithium chlorate - water mixtures

Mole fraction i\Iolar volume Coefficient of

water a t 130 OC (cc) espansion (deg-')
 CAMPBELL A N D WILLIAMS: STUDIES ON MOLTEN SALTS. I11

T A B L E I11
Analytical representation of density-temperature relation for
lithium chlorate - water ~llistures

Coefficients in eq. Coefficients in eq.

p = po esp ( - a T ) p = a - b t
Mole fraction
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T A B L E IV
Viscosity
- -

1,ithium chlorate -water misture

hlIole fractiotl Mole fraction h,Iole fraction
Pur-e lithiurn chlorate water 0.079 water 0.197 \\.ater 0.251

t ("0 ?(P) t ("C) tl(P) t ("C) tl(P) t ("C) tl(P)

i \ ~ ~ a l y t i c arepresentation
l of viscosity

r \ r r h e n i ~ ~eq.
s
q = /lo esp (GIRT) Activation energy oE
hlole fraction - viscous flolv
water '-1 0 C (licdl mole-')
--
0 000 1,979 7s 13 7 S
0.079 3.314 7124 7.1
0.197 4.144 6740 6.7
0.251 4.573 6.152 6.4

Slirface Telzrion
The surface tensions of pure molten lithium chlorate and of l n i x t ~ ~ rof
e sl i t h i ~ ~chlorate
m
\vith water and with lithium nitrate are given in Table VI. T h e surface heat of lithium
chlorate a t different temperatures, calculated from the equation I-I" = y - l7(dY/dT)
(14,1.5) was collstant at 118 erg/cm2 in the region 130 to 170 "C. The analytical representa-
tions of the temperature dependence of the surface tension of pure lithium chlorate and
of the mixtures were obtained from a least squares lit of the results of Table 1'1. The
constants of the eq~latioilare s h o ~ ~ rinn Table VII.
 CANADIAN JOURNAL O F CHEMISTRY. VOL. 42. 1964

TABLE VI
Surface tension of lithium chlorate, lithiu111 chlorate - water mixtures, and lithium
chlorate - lithium nitrate mixtures

Surface
Density tension
t ("0 (g cc-I) (dyn cm-l)
-
-

Lithium chlorate 132.1 2.0878 87.41

138.2 2.0828 87.30
142.6 2.0794 86.91
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Lithiurn chlorate - water mixtures

Mole fraction water 0.038 133.2 2.0715 86.20
139.4 2.0666 85.52
145.7 2.0617 85.10

Mole fraction water 0.090

Mole fraction water 0.155

hlole fraction water 0.236

Lithium chlorate - lithium nitrate

Mole fraction lithium nitrate 0.032

h'Iole fraction lithium nitrate 0.075 132.0

138.2
143.6

Mole fraction lithi11111nitrate 0.172 133.0

139.7
147.5
156.0
161.6
RIole fraction lithiu111nitrate 0.213 130.5
 CAMPBELL AND WILLIAMS: STUDIES O N MOLTEN SALTS. 111

T A B L E VII
Analytical representation of the surface tension variation with
temperature for lithium chlorate, lithium chlorate -water, and lithium
chlorate - lithium nitrate ~nixtures

E q . of general type
?=a-bt
Mole fraction
Additive additive a b
Pure salt
Water
\\later
Water
13.6X lo-?
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Water 0.236 101.7

Lithium nitrate 0.032 94.9 4.6X10-?
Lithium nitrate 0.075 97.4 5.6X10-?
Lithium nitrate 0.172 97.7 4.4XlO-"
Lithium nitrate 0.213 100.5 6.0X10-?

The surface tension of an equimolar mixture of lithium chlorate and water was deter-
mined a t 132.4 OC and found to be 78.4 dyn cm-', using a density calculated froin the
mixture rule and the densities of the pure components a t the temperature of determina-
tion. The surface tension of this mixture can be calculated from an ideal surface tension
relationship proposed by Guggenheiin (3).
kT A6a
y = 7 - - log cosh --
a 2kT
+
where 7 = $ ( y A y B ) , A = y:, - yn and a = area per molecule. Using this relation,
the ideal surface tension of the mixture is found to be 69.8 dyn cm-I.* I t is obvious t h a t
the above relation gives the surface tension of the mixture as being equal to the arith-
metic mean surface tension of the two liquids, minus a correction factor. This correction
factor will not be very large, unless ( a ) the difference between the surface tensions of the
two liquids is very great, ( b ) the temperature is very low on the Kelvin scale, or (c) there
is a great difference between the surface areas per molecule. In the present case, ( a ) is
not large and ( b ) not small, so that the value of the factor is determined by 6a, the differ-
ence between the surface areas per molecule. This difference is obtained as follows: If we
take the densities, a t 132.4 "C, of lithium chlorate and of water as 2.0863 and 0.9331,
respectively, the molar volunles are 43.33 n ~ andl 19.31 ml, respectively. If these volumes
are corrected for the free space in closest packing, they result as 32.06 and 14.29, respec-
tively, but it inakes very little difference to the end result whether this is done or not.
When we divide by the Avogadro number, the molecular volun~esare 5.317 X lopg3and
2.370 X cm3, respectively. If we assume the lnolecules to be spherical, the radii
are 2.330 X and 1.785 X 10-8 cm, respectively. The hemispherical surfaces of such
molecules are 3.412 X 10-l5 and 2.002 X 10-l5 cn12, respectively. Hence 6a = 1.410 X
10-lQcln?. The surface tension of lithium chlorate a t 132.4 OC is 87.41 dynjcm and that
of water, by a slight extrapolation from the figure for 130 OC, is 52.36 dynjcm. Hence
A = 35.05. With the iilsertion of these values, together with the value of the Boltzlnann
constant, the value of the correction factor is 0.11. If the correction in nlolar volume for
the free volunle is not made, the correction factor is 0.15. Hence the calculated value of the
surface tension of an equiinolecular mixture is found to be 69.8, while the experimental
value is 78.4.
*For a n ideal liquid pair, lhis relation simplifies to -y = 7-A (6a/SkT).
 1784 CANADIAN JOURNAL O F CI-IEMISTRY.VOL. 42, 196-1

DISCUSSION OF RESULTS
The density of lithium chlorate a t 131.8 "C, 2.0880 g cc-I, agrees with the earlier
result of Campbell, I<artz~nark,and Patterson (4). T h e value of Klotschko and Grigorje\\r
(5), (1.998 a t 128") is low, probably because of the presence of water in this highly 11)-gro-
scopic salt. T h e relation between the density and temperature of molten l i t h i ~ ~chlorate
ln
can be expressed by either of the following equations

P = 2.463 exp (-4.12 X 10-"T or p = 2.188 - 7.672 X lo-".

T h e general trend of increasing density in the series, chloride-nitrate-chlorate, n - l ~ i c lis~

observed wit11 sodium and potassium salts, applies also to the comparable lithium salts.
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T h e density of 1ithiul-n clllorate - water lnixtures decreases ~ v i t hincreasing water content.

T h e densitj7-temperature variation of these mixtures is represented by equations of the
same forin as those applicable to pure lithiunl chlorate. The deviation from the ideal linear
relation between molar volume and inole fraction ( ( 3 , 7, 8) is negligible for the mixtures
studied (Fig. 2). Since large deviations have been fouild for sj.stems in which complex

MOLE FRACTION
FIG.2. Molar volume at 130 OC vs. lllole fractio~lwater.

formation occurs (9, 10, l l ) , it appears that there is little immediate associatioil bet\\-een
the water and the lithium chlorate. The decrease in the coefficient of expcunsion a ~ v i t h
increase in water content inay be clue in part to an increase in the overall ionic character
of the melt. X graph of the coefficient of expansion against mole fi-action of water (Fig. 3)
sho~vsthis effect graphicall\-. T h e viscosity of pure molten lithium chlorate call be reprc-
sented in its temperature variation by

77 = 1.979 X 10-j exp (7813/11T).

T h e value of the viscosity a t 131.8 "C, viz. 33.0 cP, is slightly larger than that obtained b ~ -
Campbell, Kartzmarl;, and Patterson (4), perl~apsbecause of the inlproved technique
o Grigorjew (5) report a value of 32.3
we are now using. On the other hand, K l o t s c l ~ l ~and
cP, almost twice the value obtained by us. There is little doubt that the value of Iilotschlio
and Grigorjew is inaccurate. We suggest as the most probable cause of this discrcpanc)-
 C.\MPBELL .ASD WILLItIMS: STUDIES ON MOLTES SALTS. 111
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3.6 1 I I I I I

0.00 0.05 0.10 0.15 0.20 0.25

MOLE FRACTION
FIG.3. Coefficient of expansion vs. mole fraction water.

the fact t h a t tlie Russian workers took no precautions t o exclude from their viscometer
any decomposition proclucts, fornled in the sealing of the apparatus. We have obviated
this c1ifficult)r by including in tlie visco~ileteritself a sintered glass disc, so t h a t the fluid
can be filtered as often as desired after sealing (2). If this is not clone, tlie flow tinles are
most erratic, because the capillary of the instrument is more or less cho1;ecI with i~isoluble
decomposition products.
The viscositj- of 1l1oltei1lithium chlorate is m~1c11larger than t h a t of simple ionic salts
a t correspoiicli~igteliiperatures (i.e. taking tlie melting point of the salt, on tlie Icelvin
scale, as the basis of comparison): e.g. the viscosity of silver nitrate is 2.3 c P a t 450 OC
against 15 c P for lithium chlorate a t 168 OC. Zinc cliloricle exhibits the very high viscosit\-
of 350 c P a t 400 " C , but this is iilterpreted on the basis of a model in \\rliich fragments of
tlie original double layers of crystalline ZllClr, together wit11 ZnC16-.' ions, are the pre-
clolninant species. A 1narl;ed decrease wit11 teinperature of the activatioil energ)- for
viscous flo\v is observed for such viscous melts but this is not observecl for lithium chlorate,
the activation energy being almost constant a t 7.8 lccal mole-l between 130 and 170 "C.
This is within the range of activation energy of viscous flow for most ionic melts, viz.
3-10 1;cal mole+.
Yaffe and van Artsdalen (8) consider t h a t the heat of activatio~lfor viscous flow is
dependent on two opposing factors. As a melt expands with rising temperature, tlie total
coulombic forces among the constituent ions telid t o decrease and hence tlie activation
energy for mass inigration also decreases. Opposing this effect and because of the illcrease
in the nuliiber of holes in the melt, the average number of nearest neighbors to a given
ion may clecrease, and hence increase the attractive force per nearest neighbor, with
consequent increasing activation energy. In melts in .~\rhichthere is a large disparity in
ionic size, such as l i t h i ~ ~chlorate,
m the latter effect sho~~lcl
predominate. In fact, ho\vever,
little change is observed in the activation energy of lithium chlorate: this may be clue t o
the association in the melt brealcing do\\~nas the t e ~ i l p e r a t ~ ~rises.
r e If this is so, f e n w
b o ~ ~ cwill
l s be brolcen in mass transfer a t higher temperatures, and this ma>-compensate
for the increase in ion-neighbor attractive forces caused by a decrease in c o o r d i ~ ~ a t i o ~ ~
nunlber.
 1786 CANADIAN JOURNAL O F CIIEMISTRY. VOL. 42, 19G4

The addition of water to a lithium chlorate melt causes a considerable decrease in the
viscosity of the melt. A t temperatures slightly above the melting point, the decrease
followiilg the initial addition of water is greater than t h a t caused b y subsequent additions:
a t higher temperatures this large difference is not so marked.
Over the temperature range investigated, the viscosity isotherm for each mixture
shotvs a negative deviation from linear dependence on molar composition. Harrap and
He)-mann (12) have found t h a t this negative deviation is exhibited by all molten salts,
regardless of type.
T h e viscosity-temperature relationship for lithium chlorate -water mixtures is repre-
sented by the Arrhenius equations of Table V. T h e activation energy of viscous flow
becomes considerably sillaller as the water content increases. T h e decrease of activation
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energy is not a linear function of the inole fraction of water. T h e initial rate of change
decreases as water content increases and this indicates t h a t the average size of the mass
unit of viscous flow becomes smaller as water is added.
At teinperatures slightly above the melting point, and a t which, therefore, associated
groups may be present ill the melt, the effect of water addition on viscosity is pronounced,
probably because of the immediate break-up of these groups. A t higher temperatures,
where associated groups do not exist or exist only t o a lesser extent, water additions lower
the viscosity t o a lesser extent. T h e changes of activation energy may be interpreted in
the same way.
T h e surface tension of lithium chlorate is typical of group I salts of polyatoinic anions.
If association occurs within a melt, the associated groups will probably affect the surface
energy of the melt considerably, a n d , if these "associates" lower the surface energy, they
will be preferentially adsorbed a t the surface. T h e surface tensions of all group I nitrates
are observed t o be about the same. T h e surface tension of lithiuin chlorate a t its melting
point, 88.6 dyn clllrl, is much the same as t h a t of potassium chlorate a t its melting point,
81.0 dyn cm-I (13). If it is true t h a t the anion determines the surface energy of the group I
chlorates, a s the nitrate ion does t h a t of the group I nitrates, then it is possible t h a t in
these melts the anions pack in contact, with the cations in crevices where their effect on
surface tension is slight.
T h e surface heat, H" 7 - T(dr/dT) is not temperature dependent: it is thought to
provide a measure of the covalent character of the melt (14). For nonpolar liquids the
surface heat varies between 40 and G5 erg cm-?. Salts which are essentially ionic have the
highest values, e.g. sodium chloride 216.7, whereas molten salts which consist largely of
covalent molecules have lower values, approaching those of non-polar liquids, e.g. mag-
nesiuill chloride 76.7. T h e surface heat of lithiuin chlorate is 118 erg cm-" intermediate
between the values for ionic ~ n e l t sand those of covalent melts, and indicates t h a t a t least
soine covalent character exists in the lithium chlorate melt.
T h e temperature coefficient of inolecular surface energy is found t o be 0.468. Although
the calculation has little meaning, since lithium chlorate decomposes a t temperatures not
much above the melting point, we have used this coefficient t o find a hypothetical critical
temperature (L 17) for lithiuln chlorate, assuming, of course, t h a t the so-called "Law"
of Eotvos is applicable, viz. t h a t inolecular surface energy is a straight line fuilction of
temperature u p t o the critical temperature. T h e figure obtained is 2430 "C.
T h e surface tension of pure lithium chlorate and also those of the mixtures with water
and with lithiuin nitrate decrease linearly with teinperature. A t any fixed teinperature,
the lithiurn chlorate - lithium nitrate mixtures have surface tensions greater than t h a t of
pure lithium chlorate, while the mixtures with water have surface tensions lower than
 C.4h.IPBELL AND WILLIAMS: STUDIES ON MOLTEN SALTS. 111 1787

that of lithium chlorate. This, however, is an almost necessary consequence of the fact
that the surface tension of water a t , say, 130 "C is lower than that of lithium chlorate
while that of lithium nitrate (extrapolated for the supercooled state) is higher (126.0 dyn).
The relation between the isothermal surface tension and mole fraction of either lithiuin
nitrate or water is not linear. Initial additions up to 0.05 mole fraction affect the surface
tension of the melt to a greater extent than subsequent additions, both for lithium nitrate
and water.
The temperature coefficient of surface tension changes considerably as the water content
of the misture increases. The temperature coefficient of water is inuch higher than that
of moltell salts and this accounts for the increase of the temperature coefficient of surface
tension when water is added to molten lithium chlorate. On the other hand, the tem-
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perature coefficient of lithiuin nitrate is alrnost the saine as that of lithiunl chlorate and
this accounts for the observed fact that the addition of lithiurn nitrate hardly affects the
temperature coefficient of lithium chlorate.
The surface tension of an ideal equimolecular mixture of lithium chlorate and water
(calculated by Guggenheirn's relation (3) 69.8 dyn cm-I) is quite different from the
experimental value (78.4). Hence the melt is not ideal with respect to surface tension
behavior, a t higher concentrations of water.

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