The efficiency of chlorine evolution in dilute brines on ruthenium dioxide electrodes

Kuhn, A. T.; Mortimer, C. J.

doi:10.1007/bf00615275

Cited by 45 publications

(32 citation statements)

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“…On the other hand, Kuhn et al stated the chlorate formation reaction as a main source of oxygen (19,20). They emphasized the less noble potential of the OCTA at zero current compared to the reversible potential for the chlorine-chloride electrode system in dilute solutions of chloride.…”

Section: Hzo --O2 + 4h + + 4e [2]mentioning

confidence: 98%

Electrochemical Behavior of the Oxide‐Coated Metal Anodes

Hine

Yasuda

Noda

et al. 1979

J. Electrochem. Soc.

140

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Polarization measurement and an accelerated life test of the oxide-coated titanium anodes in relatively dilute solutions of NaCl and in HClO4 solution were conducted. The OCTA failed at potentials higher than 1.3V vs. SCE, probably due to anodic oxidation of RuO2 and passivation of Ti substrate. An accelerated life test based on those results has been investigated to estimate the OCTA. The polarizing current decreases quickly when the OCTA becomes inactive, and the service life of material is evaluated by the time-to-failure from the start-up.A n u m b e r of the oxide-coated titanium anodes (OCTA) consisting of RuO2 and TiO~ are being used because of durability and low chlorine overvoltage in chlor-alkali cells. But eventually the OCTA becomes inactive and a part of the oxide drops out (arrow in Fig. 1). Low oxygen overvoltage is another problem for this oxide anode in chlorine cells.The OCTA is stable and its chlorine overvoltage is p r e f e r a b l y low in concentrated NaC1 solutions even a t high current densities, whereas it is attacked g r a d u a l l y and the anode potential becomes high in dilute N a C 1 solutions.Since the OCTA has come into the m a r k e t in early 1970's, m a n y articles on its preparation, modification, physico-chemical properties, electrochemical characteristics, and applications have been published. Degradation and deactivation of its unique material have also been discussed. With those articles and patents, degradation of the OCTA in chlor-alkali cells can be classified into three types: (i) coating dissolution, (ii) substrate a t t a c k , and (iii) substrate oxidation leading to electrical insulation, as stated by W a r r e n et al., who have studied the P t -I r alloy coated anodes for chlorate cells (1, 2).Extensive studies on the OCTA as well as the solid Ru metal anodes in sulfuric acid solution and solid p o l y m e r electrolyte have been conducted as a part of new developments in high-performance water electrolysis. Low oxygen overvoltage of those materials is a reason. However, dissolution a n d / o r degradation of the anode material at high potential ranges, and hence at high current densities, is a problem (3).Experiment of the OCTA under the operating conditions of chlorine cells are time-consuming, about one y e a r or more for only one run. Consequently, this paper deals mainly~with an accelerated life test and its procedure for the OCTA. The procedure is simple and requires minimum labor even for a prolonged period. The test specimen of the OCTA is electrolyzed in a mixed solution of HC104 and NaCI or in HC104 single solution under a constant terminal voltage, and the current is recorded until the test specimen breaks down. The concept is based on gradual degradation of the active material due to oxygen evolution. ExperimentsTest specimen.--Titanium sheet of 5 m m wide, about 150 m m long, and 0.5 m m thick was pickled with 10% oxalic acid at about 80~ for about 3 hr, rinsed Fig. I. SEM photograph ot degraded surface of OCTA 1439 ) unless CC License in place (s...

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Section: Hzo --O2 + 4h + + 4e [2]mentioning

confidence: 98%

Electrochemical Behavior of the Oxide‐Coated Metal Anodes

Hine

Yasuda

Noda

et al. 1979

J. Electrochem. Soc.

140

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“…Already in the first publications concerning evolution of chlorine at DSA [337,342,343] (see also [344][345][346][347][348][349][350][351][352]), the authors indicated a low overpotential and a low Tafel slope. However, some methodical drawbacks (indefinite and varying partial pressure of chlorine inside the cell, inadequate methods of elimination of ohmic drops and diffusion limitations, etc.)…”

Section: Dioxide Anodesmentioning

confidence: 99%

Charge Transfer Reactions in Electrochemical and Chemical Processes

Krishtalik

1986

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“…(79)(80)(81)(82)(83)(84)(85)(86)(87)(88) Some features of the Ru0 2 coated Ti anodes have also been described. (89.90) The thermal decomposition of the coating agent to form the mixture of Ru0 2 and Ti0 2 takes place at 20~OO°C in air, depending on the paint composition, and is an exothermic reaction.…”

Section: Example 3: the Oxide-coated Metal Anodesmentioning

confidence: 99%

Electrode Processes and Electrochemical Engineering

Hine¹

1985

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No part of this book may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, microfilming, recording, or otherwise, without written permission from the Publisher FOREWORD This book has been planned and written by Dr. Hine with his knowledge and experience in electrochemical science and engineering for over thirty years since he joined with me at Kyoto University in 1948.This book is unique and is useful for engineers as well as scientists who are going to work in any interdisciplinary field connected with electrochemistry.Science is sure to clarify the truth of nature as well as bring prosperity and an improvement to the welfare of human beings. The origin of the word "science" is the same as of "conscience," which means the truth of our heart.When we consider a scientific and technological subject, first we classify it into the components and/or factors involved, and then we clarify them individually. Second, we combine them to grasp the whole meaning and feature of the subject under discussion. Computers may help us greatly, but how to establish the software that will be most desirable for our purposes is of great importance. We need to make these efforts ourselves, and not decorate with borrowed plumes.With this concept in mind, this book is attractive because the author describes the basic science in electrochemistry and practice, and discusses the electrochemical engineering applications as a combination of science and technology.Furthermore, Dr. Hine discusses the present situation and future trends in the industry with a number of drawings and photographs. He also tries to compare the electrochemical process to other competitive processes. He does this well because he has experience both in the field of science and in chemical process industries. Also, he is very happy that he has many friends worldwide who give him useful information and ideas.Dr. Hine attended classes in electrical engineering at the technical college in Osaka, then he came to my laboratory at the Department of Industrial Chemistry, Kyoto University, where he received his doctorate degree. He has studied hard and specialized in electrochemical engineering. This book is the fruit of his efforts. v vi FOREWORD It is a pleasure to provide these introductory remarks for Fumio Hine, who is so willing to work actively with an international sense. SHINZO OKADA

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The efficiency of chlorine evolution in dilute brines on ruthenium dioxide electrodes

Cited by 45 publications

References 6 publications

Electrochemical Behavior of the Oxide‐Coated Metal Anodes

Electrochemical Behavior of the Oxide‐Coated Metal Anodes

Charge Transfer Reactions in Electrochemical and Chemical Processes

Electrode Processes and Electrochemical Engineering

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