Inorganic Electrosynthesis

Ibl, N.; Vogt, Helmut

doi:10.1007/978-1-4684-3785-0_3

Cited by 32 publications

(56 citation statements)

References 138 publications

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“…In dichromate free solution the maximum rate occurs at a pH value 0.3 units below the pK h value (Ibl and Vogt, 1981) -in this work at pH 6.5. At this pH, referred to as the optimum pH by Ibl and Vogt (1981) Fig.…”

Section: Apparent Reaction Order and Optimum Reaction Phmentioning

confidence: 98%

“…In the reaction volume, generally confined in direct connection to the electrodes, the major fraction of the hypochlorite species disproportionate to chlorate according to the commonly accepted stoichiometry (Vogt et al, 2010;Colman and Tilak, 1995;Ibl and Vogt, 1981):…”

Section: Introductionmentioning

confidence: 99%

“…The global production capacity of sodium chlorate exceeded 4 Million tons 2012 (Sodium Chlorate, Chemical Engineer's Handbook, 2012). Comprehensive reviews describing the process and its chemistry have been compiled by Vogt et al (2010), Colman and Tilak (1995) and Ibl and Vogt (1981), for instance. Chlorate is produced in an electrolyte that besides the main constituents chloride and chlorate also contains small amounts of hexavalent chromium, Cr(VI).…”

Section: Introductionmentioning

confidence: 99%

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The catalyzing effect of chromate in the chlorate formation reaction

Wanngard¹,

Wildlock²

2017

Chemical Engineering Research and Design

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Section: Apparent Reaction Order and Optimum Reaction Phmentioning

confidence: 98%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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The catalyzing effect of chromate in the chlorate formation reaction

Wanngard¹,

Wildlock²

2017

Chemical Engineering Research and Design

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“…On the other hand, electrolysis of sodium chloride to produce hypochlorite solutions has been studied in detail (Ibl and Vogt 1981). It is well known that the current efficiency for hypochlorite formation is dependent on various factors, including the concentration of sodium chloride (which affects mass transfer and reaction rate at the anode) and hypochlorite (which decomposes at the anode, cathode, and bulk), current density, and temperature.…”

Section: Resultsmentioning

confidence: 99%

“…An increase in the electric current and current density at a constant flow rate and a decrease of the flow rate at a constant electric current decreased the current efficiency. The main reason for this was the increase in sodium hypochlorite concentration and its decomposition at the anode and cathode (Ibl and Vogt 1981).…”

Section: The Effect Of Variables On Current Efficiencymentioning

confidence: 99%

Chemical Recovery in TEMPO Oxidation

Kuutti¹,

Pajari²,

Rovio³

et al. 2016

BioResources

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To be regarded as environmentally friendly and economical, an industrial process using 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO) oxidation requires recycling and/or recovery of chemicals. In this work, hypochlorite recycling via electrolysis was evaluated and potential means for TEMPO recovery were explored. The most important variable affecting electrochemical hypochlorite conversion was the concentration of sodium chloride in the feed solution. With 30 g/L NaCl salt, a sufficient hypochlorite concentration of 0.8% could be obtained for pulp oxidation of up to 5% consistency. The regeneration of hypochlorite in the treated TEMPO solution was possible by electrolysis and further oxidation performed with only a small addition of make-up chemicals. During electrolysis, some TEMPO degradation took place; therefore, recovery of TEMPO should be done prior to electrolysis. For the recovery of TEMPO, solid phase extraction (SPE) was tested. The best recovery of TEMPO was obtained using a combination of hydrophobic SPE resin material and distillation (yields between 52% and 87%).

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Exploring the Mechanism of Cr(VI) Catalyzed Hypochlorous Acid Decomposition**

Busch

Simic²,

Ahlberg

2022

ChemCatChem

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Chlorate is produced through electrolysis of a chloride containing electrolyte in an undivided cell. Cr(VI) is added to the electrolyte in order to minimize the amount of oxygen formed through the homogeneous decomposition of hypochlorite. Despite the importance of Cr(VI) for the chlorate process we posses only very limited knowledge regarding the active Cr(VI) species and mechanisms through which it aids chlorate formation and inhibits O 2 evolution. Using density functional theory (DFT) modeling we present for the first time a detailed reaction mechanism for the chromate catalyzed chlorate formation. Our calculations indicate, that the reaction is initialized by the formation of a Cr(VI)-OÀ ClOCl species which forms Cr(VI)-OClO intermediate. This step is found to be rate determining with a rate constant which is comparable to the disproportionation reaction without catalyst. Chlorate is then obtained either through an uncatalyzed oxidation of chlorite to chlorate or the nucleophilic attack of OCl À followed by a second Cl À elimination step. The comparison of the activity of the different Cr(VI) species reveals that only CrO 4 2À is active whereas HCrO 4À and Cr 2 O 7 2À display sluggish kinetics.[a] M.

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Inorganic Electrosynthesis

Cited by 32 publications

References 138 publications

The catalyzing effect of chromate in the chlorate formation reaction

The catalyzing effect of chromate in the chlorate formation reaction

Chemical Recovery in TEMPO Oxidation

Exploring the Mechanism of Cr(VI) Catalyzed Hypochlorous Acid Decomposition**

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