Zur Kenntniss der Beziehungen der unterchlorigsauren Salze zu den chlorsauren Salzen

Foerster, F.; Jorre, F.

doi:10.1002/prac.18990590106

Cited by 36 publications

(13 citation statements)

References 10 publications

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“…The mechanism proposed by Foerster [1] has been confirmed recently [2] and is now generally accepted:…”

Section: Introductionmentioning

confidence: 82%

Chlorate electrosynthesis current efficiency equations based on dimensionless groups

Vogt

1992

J Appl Electrochem

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Various mathematical models for the electrosynthesis of chlorate are anatysed taking into account that the current efficiency is mainly affected by the distribution of the two competing reactions forming chlorate, i.e. the anodic oxidation and the autoxidation of hypochlorite. It is shown that the current efficiency is determined by four dimensionless groups one of which is commonly negligible. Results are compared with a known current efficiency equation. Two new current efficiency equations, representing the limiting operating conditions of chlorate systems, are proposed for industrial application.

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“…The mechanism proposed by Foerster [1] has been confirmed recently [2] and is now generally accepted:…”

Section: Introductionmentioning

confidence: 82%

Chlorate electrosynthesis current efficiency equations based on dimensionless groups

Vogt

1992

J Appl Electrochem

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“…In order to minimize losses in the process sodium dichromate is added to the electrolyte. Its use is well known since the end of the 19th century and addition of sodium dichromate to the process increases the current efficiency significantly [2][3][4]. Work has been done to understand the role of dichromate in the process and it appears to be reduced forming a thin Cr (III) film on the cathode.…”

Section: Introductionmentioning

confidence: 99%

Study of Hypochlorite Reduction Related to the Sodium Chlorate Process

et al. 2016

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Reduction of hypochlorite is the most important side reaction in the sodium chlorate reactor leading to high energy losses. Today chromate is added to the reactor solution to minimize the hypochlorite reduction but a replacement is necessary due to health and environmental risks with chromate. In order to understand the effect of different substrates on the hypochlorite reduction, α-FeOOH, γ-FeOOH, Cr 2 O 3 and CrOH 3 were electrodeposited on titanium and subjected to electrochemical investigations. These substances are commonly found on cathodes in the chlorate process and can serve as model substances for the experimental investigation. The mechanism of hypochlorite reduction was also studied using DFT calculations in which the reaction at Fe(III) and Cr(III) surface sites were considered in order to single out the electrocatalytic properties. The experimental results clearly demonstrated that the chromium films completely block the reduction of hypochlorite, while for the iron oxyhydroxides the process can readily occur. Since the electrocatalytic properties per se were shown by the DFT calculations to be very similar for Fe(III) and Cr(III) sites in the oxide matrix, other explanations for the blocking ability of chromium films are addressed and discussed in the context of surface charging, reduction of anions and conduction in the deposited films. The main conclusion is that the combined effect of electronic properties and reduction of negatively charged ions can explain the reduction kinetics of hypochlorite and the effect of chromate in the chlorate process.

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“…Originally, all cells were operated with an alkaline electrolyte until J. Landin added chromic acid to the electrolyte and solved the problem of cathodic hypochlorite reduction [4], [5]. Within the few years before and after 1900, scientific research focused on the mechanism of chlorate formation [6][7][8][9][10][11][12]; this was supplemented by numerous investigations within the last 30 years. However, the detailed reaction mechanism is still a subject of scientific debate.…”

Section: Introductionmentioning

confidence: 99%