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IBS XBOPPIHG GALLIUM ELECTRODE
II PUSBD SALTS
APPROVES;
^ u
fjci .Professor
f > / si ,? " 7 //f--)
A/* , K ^ " " in' Ill I wi*i|Mpii)wiifiiwi'wwlfe'r>n» vrliriiiiitiiiiini' -inirfwnimnrfSnwr inmnmirii i fwirriir irnilrrr-iiir-TrriTir--iiiir(irvirr-rfrVmiiirf"rifiiti
linor professor I/1:
"TF
. , / , S i i i l f t T w V i i l l * l l i l < ! I III. I I j i t f t ^ i i w H g i l i Ill
Dira ton-jof the Department of Cfaemistry
Dean of the Graduate School'
THE DROPPING GALLIUM SLECTROUE
II FUSED SALTS
THESIS
Presented to the Graduate Council of the
North Texas State University in Partial
fulfillment of the Requirements
for the Degree of
MASTSR OF SCIEHCE
By
D. Kent Dickie, A,
Denton, Texas
January, 1966
TABLE OF CONTESTS
Page
LIST Of ILLUSTRATIONS . iv
Olaapter
I. INTRODUCTION . 1
II, EXPERIMENTAL PROCEDURE . . . . . . . 7
III. RESULTS AJTC) DISCUSSION 13
BIBLIOGRAPHY . . . . . . . . . . . 27
i i i
LIST Of ILLUSTRATIONS
Figure Page
1. TJi© Dropping Gallium Electrode 9
2* Current-voltage Curve for Dropping Gallium Electrode vs. P"t Reference • in LISO3-IIO3 Eutectic at 180°C U
3. Current-voltage Curve for Dropping Mercury Electrode va Pt Reference in LHO3-KIO3 Butectic at 180°C 15
4. Current-voltage Curve for Dropping Gallium Electrode vs Pt Reference in LiCl-KCL Eutectic aST450°C 17
5. Polarographic Wave for LINO3-KHO3 Eutectic Containing Gallium Nitrate and Nitric Acid . . 19
6. Polarographic Wave for LINO3-KNO3 Eutectic Containing Lead (II) . . . 21
7. Heyrovaky-Ilkovic Plot for Data Obtained From Polarogram of I1UO3-IIO3 Eutectic Con-taining Lead (II) . 22
iv
CHAPTER I
INTRODUCTION
In 1922, Heyrovsky (9) provided a novel interpretation
of the current-potential carves observed for the dropping
mercury electrode (DEB). Most important in this interpre-
tation was the establishment that the limiting current
varies direotly in proportion to the concentration of the
solution
kd = kC.
Initially, this method was an empirical procedure*
In time it was supplemented with a quantitative theory
which made possible the interpretation of current-potential
curves by means of physical concepts related to diffusion in
the electrolyte and characteristics of the mercury drop.
This new field of electrochemistry was called polarography.
While current-potential curves can be measured with a
solid platinum microelectrode, the electrode lacks several
of the advantages of the MS* The 1MB reaches a steady
state more rapidly after a change in potential? the freeh
exposure of electrode surface allows the current to be in-
dependent of the previous history of the electrode, and the
current-potential curves obtained with the DIE can be treated
mathematically more eaaily by the Heyrovsky-Ilkovic equations
1
b M B - sl/2 - H l o g|!
where Rf equals .059 volts at T 298°K, a equals the electron -f
change, % equal® the diffusion current, and BTMB ®»d i e$ual
the applied voltage- and resulting current respectively.
Us© of the DUB in fused salts was reported in 1943 by
Steinberg and lachtrieb (10) who reported reduction waves for
Hi*"* , Cu**, Bi++ in the IH4IO3- MIO3-SH4OI eutectio at 86°G.
Steinberg and Eachtrieb (11) reported in 1950 that reduction
wa' es for Hi** , Cd+*, Zn++, and Fb , obtained with the M B
in LiHOj-KMO^-lalOj eutectlc at 160°C, obeyed the Ilkovio
equation. Christie and Qsteryoung (2) utilised the 1MB for
a polarographic study of the ciiloro-complexes of PbHi 4" 4",
and Cd** in th® LiNO -KIO eutectic at 180°C. Suzuki and co-
workers (12) have reported M B polarography in the LiCl-KCl-
A101 ©utectic at a temperature of 160°C. fell-defined re-
duction wives were reported for lb*"1", Cd**( and Zn** which
were found to obey the Ilkovic equation. Use of the M S in
fused salts is limited to investigations below about 220°C
due to the increased volatility of mercury at temperatures
above this value.
Difficulties encountered with solid electrodes (poisoning
of electrode surface and slow response to potential change)
are jasgnified in fused salts. This ha a led to investigations
of otter metals as substitutes for mercury at high temperatures,
Steinberg and Nachtrieb (11) in their work on dropping
electrode polarography in fused salts tried dropping lead
and dropping bismuth electrode® but reported these electrodes
became inoperable after several second® due to the clogging
of the capillaries. An attempt with, dropping silver in borax
at 1000°C produced erratic polarograms. Hewand Egan ($}
reported that the dropping bismuth electrode could be operated
reproducibly if the drop time was controlled by a positive
gas pressure on the liquid metal* They reported polarograms
for Cd++, Pb++, and Znt+ in the LiCl-KCl eutectic at 450°C
and a diffusion current of 5«A for the pur© melt.
Gallium, which has the unique property of being a' liquid
between 30°C and 2000°C t has been investigated by several
groups. Crabb (3), as quoted in Dissertation Abstracts# at-
tempted aqueous electr©capillary studies but reported that
the tendency for gallium to oxidise in aqueous solutions was
a Major problem. Glguer# and Lamontage (6) studied the drop-
ping gallium electrode (DGE) in aqueous solutions but found
that it behaved eratieally due to oxide formation, and pro-
duced no reproducible curves. They reported a residual
current of 50uA with a gallium drop fives times larger than
the mercury drop, lo reduction waves were attempted.
Graham (7) reported that the use of a larger oapillary
and an acidic solution overcame the oxide problem. He re-
marked that the BCKE was a useful research tool and recommended
a methanol solvent rather than water. Frumkin and co-workers
(4, 5) published several papers on electrocapillary studies
of gallium in which control of pH and voltage allowed them
to overcome the oxide problem. They found that the oxide-
forming tendencies increased as the electrode was charged
more anodioally and that it became more pronounced near the
electrocapillary maximum. Increasing the acidity of the
solutions minimized the oxidation allowing a larger voltage
span to be utilized. Pruufein (5) noted that larger errors
aay be introduced if the gallium used is of insufficient
purity. Slectr©capillary studies of gallium in fused LiCl-
KC1 have been reported by Bukum and Ukshev (1).
This gaper is an attempt to appraise the usefulness of
the D&E in fused LiNOj-KHOj, to compare it with the M B , and
to study the M B in fused LiCl-KCl.
CHAPEEB BIBLIOG-HAPHY
1. Bukun, 1. and S. Ukshev, "Electrocapillary Phenomena on Gallium in fused liCl-K01f
w ihurnal Pizicheskoi Khimii. XXXVII (1963), 1401.
2. Christie, J. 1, and R. A* Osteryoung, "Polarographic Determination of Formation Constanta of Complex Ions in Fused Journal of the American Chemical Society, LXXXII (April, 19&)), 1841.
3. Crabb, H. T., "Electrocapillary Measurements at the Gallium Electrode," unpublished dissertation, Department of Chemistry, Ohio State University, Columbus, Ohio, 1962, Dissertation Abstracts, XXII (1962), 3562-3364.
4. Frumkin, A.t 1. Grigriev, and I, Bagotateyn, "Electro-capillary Measurements Using the Gouy Capillary Electrometer," Doklady Akademik Nauk USSR. CLVII (1964), 957-963. — '
5. Frumkin, A., J. Polianoiskaya, N. Grigoriev, and I. Bagotskayn, "Electrocapillary Phenomena on OaIlium," •Electrochiaioa Acta, X (August, 1965), 793-805*
6. Giguere, P. A. and D. Lamontage, "Polarography With a Dropping Gallium Electrode»»• Science, CXX (March, 1954), 390-392.
7. Graham, D. C., "Analytical Applications of Electrical Double Layer Measurements," Analytical Chemistry# XXX (Hovember, 1958), 1736-1741."" ^
8. Heue, R. J., and J. J. Egan, "Fused Salt Polargraphy Using a Dropping Bismuth Cathode," Journal of Electro-chemical Society, CVII (October, I960),824^53?: '
9. Heyrovsky, J., ^Processes at the Mercury Dropping Cathode," Chemicke Listy. XVI (1922), 256-271.
10. Steinberg, M. A., and 1. H. lachtrieb, "Characteristics of the Dropping Mercury Electrode in Fused Salts," Journal of the American Chemical Society. MX (August, 1948),
XI, Steinker in Fuse Society»
12. Suzuki, M
T M. A.f and N. H» Nachtrieb, "Polarography Salts ,n Journal of the American Chemxoal LXXII (Auguai, l55"Oj7~355S-3567.
Hidehiro, and S. Goto, "The Dropping \lA£V.*i» f m# p mm V I iiiu Q • WM Wf * XXW JJFUJ/jXZig Mercury Electrode in Molten MCI-KCI-AICI3,» Journal
focigty of Japan, Pure Chemistry Section,
CHAPIER II
EXPERIMENTAL PROCEDURE
An inert atmosphere box constructed lay S. Blickman, Inc. ,
Weehawken, lew Jersey, was used for ail M B work* Materials
were introduced into the box after the entrance port bad
been evacuated to a pressure of ten microns and flushed
with nitrogen several times. While the atmosphere was not
circulated, the box was evacuated periodically to twenty-
five microns and flushed with nitrogen three times. The
nitrogen used was nominally 99-99 per cent pure and was
used without further purification. Metallic sodium was ex-
posed in the box to remove trace impurities. As the work
progressed it became apparent that the level of oxygen and
water vapor in the box atmosphere was high enough to cause
some interference with the work, but available methods for
changing the box*s atmosphere and desiccation were not ade-
quate.
Reagent grade chemicals were used in all cases without
further treatment except drying, four hundred grams of 99.99
per cent gallium supplied by "Reanal" finomvegysaergyar
Budapest, Hungary, were available for this investigation.
About twenty-five grams of gallium were needed to produce a
polarogram. The LiNO^-KNO^ euteetic system (38.6 mole fo
7
LllO^t mp 139°C) was prepared from oven-dried materials.
After the euteotic had teen mixed and fused,, it was stored
under desiccation at room temperature for twenty-four hours
"before it was introduced into the "box. All metal ions were + «|r
added to the melt as the nitrates except Od and Ba which
were added as the chlorides; Ca** was added as the carbonate + 4 "V
and I& was added as the oxide.
She melt was contained in an eight inch Pyrex test tube
which was heated by a Vycor tube furnace (3 x 20 cm) wound
with nichrom® ribbon covered with asbestos cord, and fitted
into a larger diameter tube. A temperature of 18Q»30Ot as
measured by a mercury thermometer dipped into the melt, was
maintained by varying the potential on the nichroaie ribbon
with a rheostat. Initially, a silver-silver chloride electrode
(1) was used as a counter electrode. It consisted of silver
wire placed in a Pyrex tube containing eutectic saturated
with AgCl, and containing 3.86 milligrams of K.C1 per gram
of eutectic. This was in contact with the system through a
fritted glass disc in the end of the tube. later, a platinum
strip (8 x 50 mm) was used as a counter electrode. The liquid
electrode reservoir (see figure 1) was fabricated from Pyrex
glass.
fhe procedure required to produce M E polarograrns was
somewhat awicward and tedious. Solid eutectic was added to
the test tube and brought to furnace temperature; an approximate
6a INLET
Pt CONTACT TO Ga
TYGON CONNECTION
INLET
fig. 1—The dropping gallium el#etrode
10
amount of metal salt was added, and the system was allowed
to equilibrate. Dropping of the J3GS was initiated by positive
nitrogen pressure on the gallium contained in the reservoir.
On several occasions it was necessary to continue this pressure
to produce a uniform drop rate. When the polarograra was com-
pleted, the electrodes were removed and a sample of the melt
collected, The gallium colleoted in the tube during the
polarogram was returned to the reservoir and the melt was
then returned to the test tube. The ?yrex oapillaries varied
in length from 75 to 125 millimeters and were hand-drawn to
a bore of about 0.25 millimeters. They were fitted down to
a ground glass ball joint with Tygon tubing which facilitated
their changing when elogging occurred after several days of
use. Gleaning with aqua regia, following by a washing with
water, allowed them to be reused. Ordinary polarographic
drop time© of one to four seconds were- observed with a pres-
sure head equivalent to 90 centimeters of gallium.
Studies were also made using LiCl-KCl. The LiCl-KCl
eutectic (58.5 mole i» mp 359°G) was dried using the method
described by Maricle and Hume (2). A platinum strip (2 x 10
cm) was used as a counter electrode. The furnace was main-
tained at 450-5°C. Phosphorus pentoxide was used rather
than sodium to reduce the moisture level in the dry box. The
oapillaries used were of a smaller bore (.15mm) than those
used in the nitrate experimentation. Heavy walled Byrex test
11
tubes were used at this higher temperature because the thinner
walled Pyrex tubes proved unreliable when exposed to thermal
shock. About five grams of gallium was needed for a polar©gram*
She polarograms using the dropping mercury electrode were
run in the atmosphere with no attempt made to shield the melt.
In each run the procedure consisted of placing solid ©utectic
in a test tube and bringing it up to furnace temperature.
Polarograms were then run on the melt in the usual manner*
It was noted that flushing the melt with nitrogen for fifteen
minutes produced no visible change in the polar©grama obtained. .
All polarograms were recorded by.- a Sargent Model XXI Recording
Polarograph with a polarization rat® of 0.074 volts per minute
on a one volt apan and 0.222 volts per minute on a three volt
.span.
CHAPTER BIBLIOGRAPHY
1, Christie, J. H., and R« A. Osteryoung, "Polar©graphic Determination of Porsmtion Constants of Complex Ions in Fused Journal of th® American Chemical Society. LXXXII (April, I960), 1841-1847.
2. Maricle, D. L. and D. !• Hume, "A New Method for Preparing Uydroxlde-Pree Alkali Chloride Malta." Journal of the Electrochemical Society, CVII (April,
12
COUPTER III
RBSTOffiS AID DISCUSSION
A comparison of the residual current curves in MNO3-
KHO3 melt was made for tooth the USE and M B . The same plati-
num counter electrode m s used so that these curves could tee
compared directly (see Figure 2 and figure 3). The available
working range for the DGE (0.1V —•* - 1.24V vs J&uch
larger than the available working rang© for the USE {-O.06-*
— 55? va Pt). The electrocapillary maximum was .04? va Pt
for the 1MB and -.4¥ vs Pt for the DGE. Frumkin and co-
workers (3) found the difference between the electrocapillary
maximum for gallium and mercury to be .42 volts in the absence
of anion adsorption on the electrode surface and .17 volts
with equal surface charge. In consideration of this, he
interpreted the .35 volts difference between the electro-
capillary maximum of mercury and gallium in chloride melt to
indicate that the predominant adsorption of anions on gallium
ia more pronounced than on mercury. Our valu® for this dif-
ference, .44 volts, using the same consideration would indicate
greater adsorption on gallium in nitrate than on gallium in
chlorides. She largest residual currents were I32«jl at-1.24
vs Pt for the DGE and 0.32j & at -0.55 vs Pt for the DME. This
much greater residual current for the DGE is due to the much
13
14
+» PI
% u 4» 0 m H 0)
rH H
Oi 9
* 8 © H
O 4* O
fl» *P # Hi p r\ • o 4B « I * KN
7 -CM *H * 0> t«0 0 •h a ft ©
© ©
1 3 ^ 8 0 0
1 5
|f f"*f EA 0 0
(vrf) lNBayno
16
|pr«ater aur facte aran of t l» iplll iM -'irop {&gpr oxiuiat«3ly
100x)« a poaeible rougi* oeetlcg of Sa203 on tha surface sf
tb® trop could gr*fitly inereaaa tb« effeotivo surface ar t*
between the wirowrj dro* and tha g a l l i w dye#.
A 'residual currant ourtm for t t» 74.C1-&C1 autaotle mm
4#tar»laa<l for tb» 3SS (aaa Figur* 4). fit® available worteitsg
raoga m e -•2S? -.73? m Pi„ a»ct the vaxiaiMft raai£uai cur-
rant wa# 23uA» a t -75Y v« J?t. Tb» alaoiroeapillary tmximxm
was looat«4 a t -*26V. $l» reaidual current varied with drop
t i»c , but the voltaga raaaiasd constant. The addition of
HbCl to the a#It produced ao visible obange in tbo residual
current curva.
?b» »ucb aaallar residual ourrant ©an be axpl&inad by
'til© aaallar dropa a t the % in t&e chloride s a l t . HIS
polcu*ograpby 'las bee;. reported by Uusimi and oo-wosrMra (?)»
but t i» atoaaae* of a aeeasia ooualiar el®otr®d® uada eanyarlaon
of tba two impractical.
On botfc « a m g a w»va ia to ba noted a t about ttoa ©site
voltage of -0 * 4? iji i?t# $&ia wava, whiob i s mtioh star® pro-
nouncad on tJaw§ BSt* s t a r t s diraotly a f t a r tfaa alaotraaaylllavy
o x t e w a . TM® mm appear® to be the radtuetiott of log to 902",
f l » addition of .Kg* as tkw yotaaaiuoa sa l t ommm iim mm to
diaappaar abioh can b® explained by the reaotioti
®% 1%- HO5- 10
17
m »a o
0 -#3 m 1 *i4 iH
ML o o *3 Sk4» p c$ O
# *rl • 4* &§ •°s © 0) wj , {8 H •PO •if id
m -u « jU *HI
1 ® O
a N # #
m%4 *r4 # PH «4 4$ P* pi
(vW) i N a y y n o
18
as suggested by Topol, Osteryoung, and Christie (9). Sailte
nitrate (prepared lay dissolving gallium in nitric acid and
dehydrating) when added' to the melt produced a wave whose
rising portion occurred in this same region of potential
(see figure 5). fhe wave diminished with passing time, end
the curve became indistinguishable from the residual current
curve after a period of about two hours. It appears that
the gallium nitrate formed was not free of nitric acid and
that this aoid caused the reduction wave. This can be ex-
plained by a series of reactions suggested by fopol and co-
workers (9) as follows:
2I(>3~ -» 2N02 + 1/2 0 2 + 0*
2I02 + 0S->103"* + !02~
HC2 + I02*^I03~ * 1 0 •
fh® ©volution of nitrogen oxides which was observed at tM.s
time also indicates these reactions.
2hat this melt behaves as a strong oxidizing medium can
be shown by its effect on silver. A silver-silver chloride
electrode was initially used as a reference electrode, but .
the potentials of gallium oxidation of the extracapillary
uaximum, and of the melt decomposition were not reproducible,
fhe silver-silver chloride electrode was found to have the
same potential as an oxide-coated silver wire. Also* the
wire became brittle and quite fragile after immersion in the
melt. Platinum electrodes also became visibly corroded and
19
CO
UL
IA H
(v?Y) iN3yano
20
covered with a dark oxide-like coating which dissolved in
concentrated HOI. from studies in a chloride melt it appears
that this corrosion occurs only after the platinum has been
in direst contact with gallium. After testing two similar
strips of platinum, It was found that a strip dipped in
gallium arid placed in a LiCl-KCl eutectic melt corroded
markedly in a twenty-four hour period while a strip simply
placed in the inelt did not. However, the platinum electrode
served for the duration of the experimentation with a potential
reproducibility of about 0.02 volts.
A polar©graphic study of Fb++ was attempted with the B£*E|
and a wave TO® obtained (see Figure 6) which followed the
Heyrovsky-Ilkovic equation. Plots of log ( t $ p i — ^ D G S
yield straight lines (see figure 7) with n « 1.0* 0.2 and
E 1/2 - -.4-0 - .03? vs Pt. The wave height was time dependent.
Apparently the lead ion was involved in a reaction with the
melt to produce 102 which undergoes reduction, The appearance
of nitrite oxidation with the addition of halid© iasae has been
reported by Novlk and Lyalikov (6). On several occasions a
red precipitate was noted at the surface of the melt. In one
case a sufficient amount was Isolated to obtain an X-ray dif-
fraction pattern identifiable aa Pb304. The formation of
PfrjO could be explained by the following reactions
3Pb++ + 7N03~-» N02~ + 6NO2 + PbjO# + 3/2 02.
21
cc 5.0
E DGE vs Pt REFERENCE (V)
Fig* 6—Polar ©graphic wave for MHO3-KNO3 euteotio containing toad ( I I ) .
22
-0 .40
'DGE
-0.45 -0 -50
vs Ft REFERENCE (V)
fig. 7—Heyrovsky-Ilkovio plot, for data obtained from polarograra of hiEOj-KMOj eutectic containing lead (II).
23
She lOg would have dissolved In the melt,and this solution
was indicated by the yellow color observed at this time. The
appreciable solubility of N02 in nitrate melts M a "been re-
ported (8), In a separate experiment it was noted that the
red product not appreciably soluble in the tie It and
produced no color change.
Polarograma of Cu**, 2»++, La++ +, Ba+4> , Ca*+ Tl+ , Cd* ,
and Ag + were attempted, but no other waves were obtained. Prom
electromotive force information available (4, 5) all of these
ions except Cu*+ and Ag+ should have been reduced.
Barlow (1) reported a well-defined wave in the I»iCl-KCl
eutectic at 450°C. The ourve had a half-wave potential of
-.56 volts vs Pt, and it became indistinguishable from the
melt after twenty-four hours. Analysis of samples taken
from the gallium, and »®lt used by standard aqueous polarography
showed no lead ion in the melt, and a much higher concentration
of lead ion w e found in the gallium than would be expected by
the electrode reaction. Barlow (1) postulated that this was
due to an exchange reaction between the electrode surface and
the melt. Polarograms were obtained for Sn++, $a++'% and 2n++|
but no reduction waves were observed,
Gallium is so susceptible to oxide formation that it ap-
pears that the surface of the gallium drop is oxidized by the
nitrate melt and that this oxide coating hinders the reduction
of metal species at its surface (10). The lack of an anhydrous
24-
melt would also lead to gallium oxide formation. Bertozai (2)
bag reported high, water solubility in nitrate melts.
Work on the chloride melt as well as on the nitrate a#lt
could be greatly hindered by the impurity of the gallium used*
Frumkin and co-workers (3) have shown that the value for
electrocapillary curve heights differed "by forty-one dynes
per centimeter and that the value for electrocapillary maximum
differed by almost a tenth of a volt when one compared the
values obtained with 99*9999 per cent pure gallium and 99.996
per cent pure gallium* If there is an exchange reaction oc-
curring as postulated by Barlow (1), the values obtained from
the DGE would become increasingly sore inaccurate with the
length of use.
CHAPTER BIBLIOGRAPHY
1. Barlow, J. D., "Electrolysis in MC1-K01 Euteotio With the BrOffing Gallium Electrode," unpublished report, V. 8. I. Research Participation Institute for High School Teachers, Benton, North Taxa© State University, 1965.
2. Bertozzi, G., "Water Solubility in Molten Salts,1* Intended Abstracts of the Electrothernics arid Metallury Division, The SlecTrochimTca1 Society ISpFing, 19*>5>), lo8-0L71*
3. Prumkin, A n J. ,Polianoiskaya, If. Grigoriev, and I. Bagotskayn, "Slectrocapillary Phenomena on Gallium, Electrochimica Acta, X (August, 1965), 793-805.
4. Gurovich, E. 1. and M, D. Matueeva, "Electromotive Force Series in Molter: Salts,"' Jhurnal Analiticheskoi Khimii, XXXVII (1965), 974-978. ^ ~ "" ^ ^ *
5. Laitinen, H. A. and C. H. Liu, "An Electromotive Force Series in Molten Lithium Chloride-Potassium Chloride Eutectic,* Journal of the American Chemical Society, LXXX (March, 1355) ,ToT5^LD2i:
6. Jlovik, R. M. and Yu S. Lyalikov, "Polarographic Deter-mination of Anions in Melts," Jhurnal Fizicheskoi Shiaaai, XXXIII (1962), 333-883T '
7« Suzuki, 5., M. Hidehiro and S. Goto,"The Dropping Mercury Electrode,*' Journal of the Chemical Society of Japan, Pure Chemical Section, UKSXltf (19&2),'883~88FT
8. Swafford, H. S., Jr. and P. G. McCormick, "A Yoltammetrio Study of the Oxidation of Iodide and Bromide in Potassium Hitrate-Sodium Nitrate Eutectic Melts,*1
Analytical Chemistry. XXXVII (July, 1965), 974-978.
9. Topol, I. B., J. H. Christie and R. A. Osteryoung, "Electrochemical Studies of Acid-Bases Equilibria in Molten Alkali Iitrate©,w Extended Abstracts of the Sleo trothermics and Metallury Mvision, The ETectro-oheaioai iocliTyTgprl'nE'; 207-212:
25
26
10. Wolf, Guenter, "Electrode Reactions on Solid and Liquid Gallium in Aaueous Electrolyte SolutionsZeitachrift fur Bhyaiteliscfae gfaemii, CCXXIII (1963), 2 W % W * "
BIBLIOGRAPHY
Articles
Bukun, I. and B. TJkshev, "Electrocapillary Phenomena on
Gallium in fused MC1-IC1," Zhurnal Fizicheekoi KMmli. XXXVII (1963), 1401-1409.
Christie, J. H. and R. A. Qsteryoung, "Polar©graphic Deter-mination of Formation Constanta of Complex Ions in Fused LiKOj-KNO^," Journal of the American Chemical Society. LXXXII (April, 196oI, 1841-1847.
Frumkin, A., J. Polianoiskaya, 1. Grigoriev, and I. Bagotsteyn, "Blectrocapillary Phenomena on Gallium," Sleotroohimloa Acta* X (1965), 793-805.
Frumkin, A., H, Grigoriev, and 1. Bagotskayn, "Eleotrocapillary Measurement® Using the Gouy Capillary Electrometer," Doklady Akademii Haul S8SR. CLVII (1964), 957-963.
Giguere, P. A. and B. I&aontage, «Polarography With a Dropping Gallium Electrode9
U Science. CXX (March, 1954), 390-392.
Graham, D. 0., "Analytical Application of Electrical Double layer Measurements,w Analytical Chemistry, XXX (Hoveatber, 1958), 1736.
Gurovich, 1. I. and If. D. Matueeva, "Electromotive Force Series in Molten Salts,w Jhurnal Analfiticheakol Khiimai. XXXVII (1965), 974-978.
Heu®, E. J. and J. J. Igan, "Fused Salt Polarography Using a Dropping Bismuth Cathode," Journal of the Electro-chemical Society. CVII (October, 19bOT7 S2T-533:
Heyrovsky, J., "Processes at the Mercury Dropping Cathode," Chemioke Listy. XVI (1922), 256-271.
Laitinen, H. A. and C. H. Liu, "An Electromotive Force Series in Molten lithium Chloride-Potassium Chloride Eutectic," Journal of the American Chemical Society. £XXX (March,
27
2'8
Maricle, 2). L. and D. I. Hume, "A Sew Method for Preparing Hydroxide-feee Alkali Chloride Melts," Journal of the Electrochemical Society, CVII (April,. I960), 354-359•
lovik, R. M. and Yu S« Lyalikou, "Polarographic Determination of Anions in Melts," Jhurnal Pizicheskoi Khiinmi, XXXIII (1962), 883-888.
Steinberg, 1. A. and N. H. Nachtrieb, "Characteristics of the Dropping Mercury Electrode in Fused Salts,H Journal of the American Chemical Society. M X (August, 1948), 2FT3-WE4~ 1
, "Polarography in Pused Sale's»'*""Journal of the American Chemical Society. IXXII (August, 1950), 5558-5567*
Suzuki, M., M. Hidehiro, and S. Goto, "The Dropping Mercury Electrode in Molten LiCl-KCl-AlClj," Journal of the Chemical Society of Japan. Pure Chemical Section, LXXXIII l(19i
l2)"","i"88,5«88S; ~
Swafford, H. 3., Jr., and P. G, MoCormick, WA Voltammetric Study of the Oxidation of Iodide and Bromide in Potassium Hitrate-Sodium Nitrate Eutectic Melts,« Analytical Chemistry, XXXVII (July, 1965), 974-978.
Wolf, Guenter, "Electrode Reactions on Solid and Liquid Gallium in Aqueous Electrolyte Solutions," Zeitschrjft fur Physikalisch® Chemii. CCXXIII (1963)» 249-259•
Publications of Learned Organizations
Bertozssi, G., "Water Solubility in Molten Salts," Extended Abstracts of the Electrothermics and Metallurgy Division, f m Slectrochiilcal Society (BgriBST W W ) , 118-1717
Topol, L. E., J. H. Christie, and R. A. Oateryoung, "Electro-chemical Studies of Acid-Bases Equilibria in Molten Alkali nitrates," Extended Abstracts of the Electrothermics and Metallurgy Division, lh#" llecirocEimlcal' Society (Spring, 1955); 207-212.
Unpublished Materials
Barlow, J. D., "Electrolysis in LiCl-KCl Eutectic With the Dropping Gallium Electrode," unpublished report, I. S. P. Research Participation Institute for High School feachers, Denton, North Texas State University, 1965.
29
Crabb, 1. T., "Slectrocapillary Measurements at the Gallium Electrode," unpublished dissertation, Dej>artment of Cherniatry, Ohio State University. Columbus. Ohio. 1962, Dissertation Abstracts, XXII (1962), 3362-3364*