Electrochemical study of fuming sulphuric acids : I. Kinetic parameters of the anodic and cathodic reactions on platinum electrodes
Kinetic parameters related to the anodic and cathodic processes in the electrolysis of fuming sulphuric acids on bright platinum and platinized platinum electrodes have been established, the electrolyte being kept at rest. Experiments cover temperatures from 25 to 70°C and oleums with a sulphur trio...
| Autores: | ; ; |
|---|---|
| Tipo de documento: | Artículo |
| Estado: | Published version |
| Fecha de publicación: | 1968 |
| País: | Argentina |
| Institución: | UNLP |
| Repositorio: | SEDICI (UNLP) |
| Lenguaje: | Inglés |
| OAI Identifier: | oai:sedici.unlp.edu.ar:10915/119913 |
| Acceso en línea: | http://sedici.unlp.edu.ar/handle/10915/119913 |
| Nivel de acceso: | Acceso abierto |
| Palabra clave: | Ciencias Exactas Química Fuming sulphuric acids Platinum Kinetic parameters |
| _version_ | 1878403603006226432 |
|---|---|
| author | Garrera, H. A. |
| author2 | Carrozza, Jesús Simón Arvia, Alejandro Jorge |
| author2_role | author author |
| author_browse | Arvia, Alejandro Jorge Carrozza, Jesús Simón Garrera, H. A. |
| author_facet | Garrera, H. A. Carrozza, Jesús Simón Arvia, Alejandro Jorge |
| author_role | author |
| collection | SEDICI (UNLP) |
| description | Kinetic parameters related to the anodic and cathodic processes in the electrolysis of fuming sulphuric acids on bright platinum and platinized platinum electrodes have been established, the electrolyte being kept at rest. Experiments cover temperatures from 25 to 70°C and oleums with a sulphur trioxide concentration from about 5 to 28 per cent. The yields of the different anodic and cathodic products mentioned in a previous publication have been confirmed and results for others are given. The anodic reaction is characterized by current/voltage curves which fit Tafel plots at high voltage, with a slope close to 2·3(2RT/F). The cathodic current/voltage curves plotted according to the Tafel equation exhibit three different regions. (i) At voltages lower than 0·4 V, a Tafel line with a slope of 2·3(RT/F) is observed. (ii) At about 0·5 V a limiting current is shown. These regions are related to the reduction of sulphur trioxide. (iii) At voltages larger than 0·7 V, a clear Tafel line region appears again, involving a 2·3 (2RT/F) slope. The latter is related to the evolution of hydrogen and the simultaneous presence of a blue tinge in the oleums, which is attributed to the formation of disulphur trioxide. |
| eu_rights_str_mv | openAccess |
| format | article |
| id | AR_9d9e522e2031b7a7367abb2aaed20e3f |
| institution | UNLP |
| instname_str | Universidad Nacional de La Plata |
| language | eng |
| network_acronym_str | AR |
| network_name_str | Argentina |
| oai_identifier_str | oai:sedici.unlp.edu.ar:10915/119913 |
| publishDate | 1968 |
| publishDateSort | 1968 |
| reponame_str | SEDICI (UNLP) |
| spelling | Electrochemical study of fuming sulphuric acids : I. Kinetic parameters of the anodic and cathodic reactions on platinum electrodes Garrera, H. A. Carrozza, Jesús Simón Arvia, Alejandro Jorge Ciencias Exactas Química Fuming sulphuric acids Platinum Kinetic parameters Kinetic parameters related to the anodic and cathodic processes in the electrolysis of fuming sulphuric acids on bright platinum and platinized platinum electrodes have been established, the electrolyte being kept at rest. Experiments cover temperatures from 25 to 70°C and oleums with a sulphur trioxide concentration from about 5 to 28 per cent. The yields of the different anodic and cathodic products mentioned in a previous publication have been confirmed and results for others are given. The anodic reaction is characterized by current/voltage curves which fit Tafel plots at high voltage, with a slope close to 2·3(2RT/F). The cathodic current/voltage curves plotted according to the Tafel equation exhibit three different regions. (i) At voltages lower than 0·4 V, a Tafel line with a slope of 2·3(RT/F) is observed. (ii) At about 0·5 V a limiting current is shown. These regions are related to the reduction of sulphur trioxide. (iii) At voltages larger than 0·7 V, a clear Tafel line region appears again, involving a 2·3 (2RT/F) slope. The latter is related to the evolution of hydrogen and the simultaneous presence of a blue tinge in the oleums, which is attributed to the formation of disulphur trioxide. Les paramètres cinétiques des processus anodiques et cathodiques dans l'électrolyse des oléums sur des électrodes de platine poli et platine platinisé ont été établis, l'électrolyte étant au repos. Les expériences ont été réalisées a des températures de 25 à 70°C avec une concentration de trioxyde de soufre de 5 à 28 pour cent. Les rapports des différents produits anodiques et cathodiques mentionnés dans une publication antérieure ont été confirmés; on présente aussi d'autres résultats. Les courbes courant/voltage de la réaction anodique suivent la loi de Tafel à tensions élevées, avec une pente proche de 2,3(2RT/F). Les courbes cathodiques tracées de la même façon montrent trois régions différentes. (i) A des tensions de moins de 0,4 V on observe une droite avec un pente 2,3(RT/F). (ii) A des tensions d'environ 0,5 V, on a trouvé un courant limite. Ces deux régions (i) et (ii) sont déterminées par la réduction du trioxide de soufre. (iii) A des tensions de plus de 0,7 V on a retrouvé une droite de Tafel avec une pente de 2,3(2RT/F). Celle-ci est on relation avec l'évolution de l'hydrogène et l'apparition simultanée d'une teinte bleue dans l'électrolyte, qu'on a attribuée a la formation de trioxyde de disoufre. Man ermittelte die kinetischen Parameter der Anoden- und Kathodenvorgänge bei der Elektrolyse von rauchender Schwefelsäure an Platin- und platinierten Platinelektroden in ruhendem Elektrolyten. Die Versuchstemperatur wurde zwischen 25 und 70°C, der Schwefeltrioxydegehalt des Oleums zwischen ungefähr 5 und 28 %. variiert. Die Zusammensetzung der kathodischen und anodischen Reaktionsprodukte, wie sie in einer früheren Arbeit beschrieben wurden, konnten bestätigt werden, daneben werden die Ergebnisse weiterer Versuche bekanntegegeben. Die anodische Reaktion ist gekennzeichnet durch Strom-Spannungskurven, welche bei hohen Spannungen Tafel-Charakter mit einer Steigung von beinahe 2,3(2RT/F) annehmen. Die als Tafel-Beziehungen aufgezeichneten kathodischen Strom-Spannungskurven weisen drei verschiedene Gebiete auf. (A) Bei Spannungen unterhalb von 0,4 V erhält man eine Gerade mit der Steigung 2,3(2RT/F). (B) Bei ungefähr 0,5 V tritt ein Grenzstrom auf, welcher von der Reduktion dos Schwefeltrioxyds/herrührt. (C) Bei Spannungen oberhalb 0,7 V ergibt sich wiederum eine Gerade mit deutlichem Tafel-Charakter und einer Steigung von 2,3(2RT/F). Diese dritte Zone steht in Beziehung zur Wasserstoffentwicklung und zu der gleichzeitigen Blaufärbung des Oleums, welche der Bildung von Schwefelsesquioxyd zugeschrieben wird. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas http://sedici.unlp.edu.ar/handle/10915/119913 |
| spellingShingle | Electrochemical study of fuming sulphuric acids : I. Kinetic parameters of the anodic and cathodic reactions on platinum electrodes Garrera, H. A. Ciencias Exactas Química Fuming sulphuric acids Platinum Kinetic parameters |
| status_str | publishedVersion |
| title | Electrochemical study of fuming sulphuric acids : I. Kinetic parameters of the anodic and cathodic reactions on platinum electrodes |
| title_full | Electrochemical study of fuming sulphuric acids : I. Kinetic parameters of the anodic and cathodic reactions on platinum electrodes |
| title_fullStr | Electrochemical study of fuming sulphuric acids : I. Kinetic parameters of the anodic and cathodic reactions on platinum electrodes |
| title_full_unstemmed | Electrochemical study of fuming sulphuric acids : I. Kinetic parameters of the anodic and cathodic reactions on platinum electrodes |
| title_short | Electrochemical study of fuming sulphuric acids : I. Kinetic parameters of the anodic and cathodic reactions on platinum electrodes |
| title_sort | Electrochemical study of fuming sulphuric acids : I. Kinetic parameters of the anodic and cathodic reactions on platinum electrodes |
| topic | Ciencias Exactas Química Fuming sulphuric acids Platinum Kinetic parameters |
| topic_facet | Ciencias Exactas Química Fuming sulphuric acids Platinum Kinetic parameters |
| url | http://sedici.unlp.edu.ar/handle/10915/119913 |