Coulometric preparation of standard nitrogen dioxide gas mixtures by electrolysis of molten nitrate

Yoshimori, Takayoshi; Kawahara, Hideo; Hara, T.; Ikeda, Akira

doi:10.1016/s0003-2670(01)83256-6

Cited by 4 publications

(5 citation statements)

References 5 publications

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“…[1] reaches 70 mA (220 mA/cm -~) at potentials of --0.90V, --1.36V, and --1.82V for LiNO~, NaNOz, and KNO:3, respectively. Neither the main anodic wave at about 1.1V resulting from nitrate oxidation (32)(33)(34)(35)(36)(37)(38)(39) NOB---> NO2 + 89 + e- [6] nor the anodic process having a peak potential of about +0.5V reflecting nitrite oxidation (3,18,19,38,40,41) NO2--> NO2 + e- [7] appear to be greatly affected by the nature of the cation. For LiNOs, the anodic peak due to the oxidation of Li20 to Li202 is again observed at --0.36V.…”

Section: (Dashed Line)mentioning

confidence: 99%

Cation Effects on the Electrode Reduction of Molten Nitrates

Miles

Fletcher

1980

J. Electrochem. Soc.

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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.

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Section: (Dashed Line)mentioning

confidence: 99%

Cation Effects on the Electrode Reduction of Molten Nitrates

Miles

Fletcher

1980

J. Electrochem. Soc.

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“…28,42 The gases generated were monitored with the CL NO x analyzer, which revealed that NO was generated along with NO 2 . Alternative NO 2 generation methods have been reported, including electrochemical generation 43 and photodecomposition of nitrate with an ∼300 nm UV light. 44,45 The photodecomposition system was simplified to be suitable for our purposes, but again both NO and NO 2 were observed in the generated gas.…”

Section: Resultsmentioning

confidence: 99%

“…We then tested flowing and mixing these reagents together, followed by introduction to the honeycomb-patterned microchannel gas desorber. , The gases generated were monitored with the CL NO x analyzer, which revealed that NO was generated along with NO 2 . Alternative NO 2 generation methods have been reported, including electrochemical generation and photodecomposition of nitrate with an ∼300 nm UV light. , The photodecomposition system was simplified to be suitable for our purposes, but again both NO and NO 2 were observed in the generated gas. Problems arose with side reactions in both photoinduced and chemical generation; consequently, we concluded that neither method was suitable for NO 2 generation in the aqueous phase.…”

Section: Resultsmentioning

confidence: 99%

Micro Gas Analyzer Measurement of Nitric Oxide in Breath by Direct Wet Scrubbing and Fluorescence Detection

et al. 2009

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A novel method is proposed to measure NO in breath. Breath NO is a useful diagnostic measure for asthma patients. Due to the low water solubility of NO, existing wet chemical NO measurements are conducted on NO(2) after removal of pre-existing NO(2) and conversion of NO to NO(2). In contrast, this study utilizes direct measurement of NO by wet chemistry. Gaseous NO was collected into an aqueous phase by a honeycomb-patterned microchannel scrubber and reacted with diaminofluorescein-2 (DAF-2). Fluorescence of the product was measured using a miniature detector, comprising a blue light-emitting diode (LED) and a photodiode. The response intensity was found to dramatically increase following addition of NO(2) into the absorbing solution or air sample. By optimizing the conditions, the sensitivity obtained was sufficient to measure parts per billion by volume levels of NO continuously. The system was applied to real analysis of NO in breath, and the effect of coexisting compounds was investigated. The proposed system could successfully measure breath NO.

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“…As illustrated in Fig. trates (18,19). The reversible electrode reduction of silver nitrate AgNO3 + e-~-Ag + NO3- [3] accounts for the relatively small peak observed at -0.18V.…”

Section: Results and Discussion O ~ -08mentioning

confidence: 99%

“…Other investigators have noted that AgNO3 additions affect the cathodic reactions in molten ni. trates (18,19).…”

Section: Results and Discussion O ~ -08mentioning

confidence: 99%

Reactions Involving Silver Ions and Silver Metal in Molten Nitrates

Miles¹,

McManis²,

Fletcher³

1984

J. Electrochem. Soc.

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Regarding quarternary systems, the introduction of the composition parameters y, t, and S serves in the planning of experiments and in reducing the large number of compositions to be studied in order to characterize a quarternary system adequately.Also, the use of these composition parameters makes it possible to plot thermodynamic data along well-defined composition paths and to identify the effects of competing interactions on a charge asymmetric cation. For example, the complexing effects of CsC1 or KC1 on MnCI~ become evident as the quarternary solutions become richer in CsC1, or in KC1, respectively.The successful application of Eq.[15], [16], and [17] to such nonideal charge asymmetric fused-salt solutions indicates that in quarternary, and possibly even in higher order systems, reactions within the binary solutions account for most of the internal reactivity which is responsible for deviations from ideality. Thus, the formation of a higher order system represents mixing of such prereacted binary systems and the properties of the multicomponent system should be predictable.However, it should be noted that Eq.[15], [16], and [17] are only applicable to the "acid," or higher valence, component of a charge asymmetric fused-salt mixture. ABSTRACTThe electrochemical reduction of molten LiNO3 on platinum or nickel electrodes produces insoluble LifO that passivates the cathode at high current densities. The presence of small amounts of silver ions prevents this passivation by undergoing reduction to silver metal in the form of dendritic deposits that increase the effective area of the electrode. The deposited silver is unstable in molten LiNO3 and reacts with the melt to regenerate silver ions. Corrosion studies of silver coupons gave a weight loss rate of 280 ~g h-lcm -2 in molten LiNO3 at 350~ but of only 5 ~g h-lcm -2 in KNO~ at 375~ The presence of water in the LiNO3 melt increases the corrosion rate of silver. Additions of Li20, LiNO2, LiC1, or AgNO3 to molten LiNO3 significantly decreases the corrosion rate. The addition of oxide ions to a AgNO~ containing melt produces a dark precipitate of Ag20 in NaNO~ or KNO3, but not in LiNO3. The decomposition reaction of Ag20 into its elements is kinetically slow in molten nitrates with a rate similar to that observed in air.) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 169.230.243.252 ABSTRACTThe photoelectrochemical properties of n-SiC were studied in aqueous electrolytes. The onset potential of the anodic photocurrent in steady state was found to be about 1V more anodic than that of the photocurrent measured by the lock-in method (-2V vs. SCE). This discrepancy was ascribed to the presence of transient photocurrent observed in the potential range between -1.9 and +0.6V vs. SCE. Possible mechanisms of the transient photoresponse were exam-

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Coulometric preparation of standard nitrogen dioxide gas mixtures by electrolysis of molten nitrate

Cited by 4 publications

References 5 publications

Cation Effects on the Electrode Reduction of Molten Nitrates

Cation Effects on the Electrode Reduction of Molten Nitrates

Micro Gas Analyzer Measurement of Nitric Oxide in Breath by Direct Wet Scrubbing and Fluorescence Detection

Reactions Involving Silver Ions and Silver Metal in Molten Nitrates

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