Titration of acidic cations in molten nitrates with electrolytically generated oxide ions

Bombi, G. Giorgio; Fiorani, Mario

doi:10.1016/0039-9140(65)80207-7

Cited by 27 publications

(10 citation statements)

References 2 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Manuscript submitted Sept. 4,1979; revised manuscript received Feb. 8, 1980. Any discussion of this paper will appear in a Discussion Section to be published in the June 1981 JOURNAL. All discussions for the June 1981 Discussion Section should be submitted by Feb. 1, 1981. Publication costs of this article were assisted by the Naval Weapons Center.…”

Section: Discussionmentioning

confidence: 99%

“…Oxide ions are produced by the electrochemical reduction of molten alkali metal nitrates (2)(3)(4)(5) MN'Oa + 2e-~ MNO2 + O-- [1] The role of the oxide ion produced by this reaction has been a controversial ghost which has haunted the chemistry of fused nitrates (6,7). A variety of studies (8)(9)(10)(11)(12)(13)(14)(15)(16)(17), however, support the conclusions that the oxide ion in nitrate melts is an unstable species due to the following reactions O = + NO~-~ NO2-+ 02 = [2] 02 = + 2NO~-~ 2NO2-+ 202- [3] in which the oxide is converted to peroxide or superoxide (6,18,19).…”

mentioning

confidence: 99%

“…Just as the positive electric field of a cation near a reacting species can make it more difficult to remove electrons in anodic reactions such as 20 = ~ 02 = + 2e- [4] 02 = ~ 02-+ e- [5] the cation field can also make it less difficult to add electrons in cathodic reactions such as in Eq. [1].…”

mentioning

confidence: 99%

See 2 more Smart Citations

Cation Effects on the Electrode Reduction of Molten Nitrates

Miles

Fletcher

1980

J. Electrochem. Soc.

View full text Add to dashboard Cite

Cyclic voltammetric, potentiostatic, and galvanostatic methods were used to investigate the electroreduction of molten alkali metal nitrates at 350°C on a platinum electrode. The cation of the nitrate salt plays a major role in the reduction reaction as well as in determining the ultimate fate of the oxide ion produced. Nitrate reduction occurs most readily in LiNO3 melts, and the Li2O formed appears to be relatively stable. Overvoltages for nitrate reduction increase with increasing size of the metal cation involved and the oxide ions produced by the reaction become more prone to oxidation to form peroxides or superoxides. The rate of water removal by purging the nitrate melt with helium gas was monitored by the water‐wave on platinum. Surprisingly, no water‐wave was detected using a nickel electrode. The solubilities of several substances were determined in LiNO3 and KNO3 and compared with ideal solubility calculations.

show abstract

Section: Discussionmentioning

confidence: 99%

mentioning

confidence: 99%

See 1 more Smart Citation

Cation Effects on the Electrode Reduction of Molten Nitrates

Miles

Fletcher

1980

J. Electrochem. Soc.

View full text Add to dashboard Cite

show abstract

“…Copper (II). Cu(II) is a better oxide ion acceptor in molten NaN03-KN03 than either Cd(II) or Pb(II) (18). Apparently the precipitation of CuO, more important at higher temperatures (17), has in some cases (12,13) prevented the voltammetric studies of Cu(II).…”

Section: Discussionmentioning

confidence: 99%

Linear sweep voltammetry of silver(I), cadmium(II), lead(II), copper(II), and indium(III) in molten NaNO3-KNO3 eutectic

Mamantov¹,

Strong²,

Clayton³

1968

Anal. Chem.

View full text Add to dashboard Cite

Spontaneous Decomposition of Ozone. After using solutions of ozone for some time, in the platinum ring-disk electrochemical studies described above, it was observed that the anodic currents measured for potentials more positive than 1.3 volts were larger than when the solution was fresh. Ozone was removed by bubbling nitrogen through the solution. I¡E curves obtained from the resulting ozone-free solutions were typical of those obtained in solutions of hydrogen peroxide.To establish whether the decomposition of ozone was catalyzed at the platinum electrode surface, ozone was bubbled through 1M sulfuric acid for 150 minutes, in the absence of any platinum and in the presence of a ~60-sq cm bright platinum gauze electrode. Ozone was removed by bubbling nitrogen through the solutions.The IjE curves obtained following the experiment showed that the hydrogen peroxide content was the same as that obtained in the absence of the platinum electrode and equaled 2 X 10-5M. The concentration of ozone during the experi-ment was 5 X 10-4M. Hence, the spontaneous decomposition of ozone to hydrogen peroxide is not appreciably catalyzed by a bright platinum surface.Molar Absorptivity Determination. Because of the large variations of the reported value of the molar absorptivity coefficient for ozone at 258 to 260 µ, it was redetermined with a Cary 15 spectrophotometer. Beer's law was obeyed in the concentrations range 2 X 10-s to 4 X 10-4M in a 1-cm quartz cell. A molar absorptivity coefficient of 2500 liter mole-1 cm-1 was calculated, which is in close agreement with the value of 2600 liter mole-1 cm-1 reported by Ingols, Fetner, and Eberhardt (7).

show abstract

“…A fused salt mixture containing equal parts of sodium and potassium nitrates was used as a solvent by several workers. Bombi and Fiorani (23) studied the titration of 13 cations with 02~p roduced by constant-current reduction of the nitrate melt at a platinum electrode. Schlegel (198) carbonate which produced O2-in the melt.…”

Section: Titrants and Solventsmentioning

confidence: 99%