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Electrolysis of a carbonate-borate solution with a platinum anode—I. Current efficiency at perborate concentration of zero

✍ Scribed by P.M.v.d. Wiel; L.J.J. Janssen; J.G. Hoogland


Publisher
Elsevier Science
Year
1971
Tongue
English
Weight
681 KB
Volume
16
Category
Article
ISSN
0013-4686

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✦ Synopsis


During the electrochemical preparation of perborate in carbonate-borate solutions, peroxocarbonate (CIOBB-) is formed at the platinum anode; this CaOa%-hydrolyses to HIOs in the solution. The factors affecting the current efficiency Ra at [HIO,l = 0 were investigated. The R/ [l&O,] relation and the ~/fog J curve were measured under various conditions. olation of the R/[HnO,l curve, R, was determined. By linear extrap-R, strongly increases with increasing cd until 200 mA/cma and slightly decreases above 400 mA/ cm2. Furthermore R. increases by replacing Na+ by K+ , with increasing carbonate concentration, with decreasing temperature, by rotation of the anode and by addition of fluoride at 100 mA/cma; fluoride has no influence at 400 mA/cma. The pH has no effect on R,, in the region from 9 to 12. At higher pH a strong decrease of R. occurs. Kinetic factors determine R. at current densities lower than 75 mA/cm*. current density Jo of the reaction The standard exchange 2 COsa-= CBO,*-+ 2 e is smaller than 1.5 x 1O-8 A/cm* and the transfer coefficient a is 0.3. At cd > 350 mA/cme peroxocarbonate formation is limited by diffusion of carbonate. The diffusion coefficients of carbonate ions in 1.25 M NaaCOs and 1.25 M KBCOs are respectively 2.8 x 10~~ and 3.6 x 1O-e cm*/s. R&m&Pendant la preparation Blectrochimique de perborate en milieu carbonate-borate, du peroxocarbonate (C%Osa-) est form6 sur l'anode de platine; ce C,O,a-hydrolyse & HsOp dans la solution. Les facteurs tiuant le rendement du courant R, A [H,O,] = 0 ont Btb &udi&. C'est pourquoi la relation R/[H,O,] et la courbe e/log J ont 6tb mesur&es dans des circonstances variees. R,, ktait determink par extrapolation linkire de la courbe R/[H808]. Nous avons trouv6 que R. augmente fortement en augmentant la densit de courant jusqu'h 200 mA/cmB et que R. diminue un peu en plus de 400 mA/cmP. D'alleirs nous augrnentons R. en remplapnt Na+ par K+, en augmentant la concentration du carbonate et en diminuant la temp&ature, en faisant toumer l'anode et par addition de fluorure a 100 mA/cmB; de la fluorure ne l'enfluence pas & 400 mA/cm*. Le pH ne provoque pas le R. dans la rkgion de 9 & 12. Quand le pH monte plus, & diminue fortement. Des resultats de la recherche nous avons d&iv6 que des facteurs cin&iques determinent R. ii des densites de courant moins de 75 mA/cm2. La den&t de courant d'kchange J,, de la r&action 2 COsa-,' C,O,a-+ 2 e est plus petite que 1,5 x lo-* A/cm2 et le coefficient de transfert a est 0,3. A des densitb de courant plus hautes que 350 mA/crna, la formation de peroxocarbonate est limit& par la diffusion de carbonate. Les coefficients de diffusion d'ions de carbonate en milieu I,25 M Na,CO, et 1,25 M K&O, sont respectivement 2,8 x 10-O et 3,6 x 1O-6 cm'+. Zusammenfassung-WSihrend der elektrochemischen Herstellung von Perborat in Karbonat-Borat Ltisungen wird an der Pt-Anode Peroxokarbonat Ca0,,2-gebildet; dat CaOl*-hydrolysiert im Elektrolyten zu HaOe. Es wurden die Faktoren untersucht welche die Stromausbeute R, bei [H*O,] = 0 beeitiussen. Zu dem Zweck wurden die R,/[H,Oa] Beziehung und die ~/log JKurve unter wechselnden Bedingungen gemessen. Durch lineare Extrapolation der R/[H,O,] Kurve wurde R,, ermittelt. Es wurde gefunden dass R,, stark zunimmt mit wachsender Stromdichte bis zu 200 mA/cmP urn oberhalb 400 mA/cn? wieder ein wenig abzufallen. Ferner nimmt R. zu wenn man Na+ durch K+ ersetzt, die Karbonatkonzentration erhijht, die Temperatur erniedrigt, die Anode rotiert und bei 100 mA/crna Fluoride zusetzt; Fluoride sind unwirksam bei 400 mA/cm8. Der pH-Wert im Bereich von 9-12 beeinflusst R. nicht. Bei hSheren pH-Werten nimmt R, stark ab. Aus diesen Ergebnissen wurde geschIossen dass kinetische Faktoren & bestimmen bei Stromdichten unterhalb 75 mA/cn?. Die Standardaustauschstromdichte J0 der Reaktion 2 CO,"-; C,Oaa--t-2 e * Manuscript received


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