The equilibrium potential of the cell Alup 1 NatiF, + A1808c,t, 1 Pt, 0, was determined from potential-decay curves to be 2.205 V at 1000°C. A Tafel plot of the anodic overvoltage. shows two straight portions with slopes RT/3F and RT/F, indicating a two-step discharge reaction of oxygen, with exchan
Chronopotentiometric measurements on graphite anodes in cryolite—alumina melts
✍ Scribed by J. Thonstad
- Publisher
- Elsevier Science
- Year
- 1969
- Tongue
- English
- Weight
- 569 KB
- Volume
- 14
- Category
- Article
- ISSN
- 0013-4686
No coin nor oath required. For personal study only.
✦ Synopsis
At cds above a crrtical cd, oxygen drscbarge on carbon m cryoltte-elumma melts IS l&ted bv dBuston-controlled deuletton of dtssolved alumma. followed bv the anode effect In melts wtth 2% pond6raux Al& 1+/\/C d6croit lm&irement a densite de courant crorssante pour des temps de transttion comprts entre envuon f8 et 1 ms, attetgnant une valeur constante pour des temps momdres. Ce comportement semble &re d0 B la drssocratton lente nuttale de l'alumme drssoute. La constante d'bquthbre de cette &action est trouv6e &gale ilO, et les constantes de wtesses des composantes progresswe et regressive a 1400 et 2400 S-l respecttvement. Le wet&tent de diffusion de l'alumine dtssoute vaut 1,s x 10-6cm\/S a 1020°C La relation th&onque potentJ/temps des reactions trr&erstbles est satrsfatte a des densttes de courant mferteures a + 15 A/cm\, il des denstt6s de courant sup&reures, le potenttel croft plus raptdement que p&u. m\_Dte Sauerstoffentladung an Kohle m Schmelxen von Kryol~th/Alummtumoxyd 1st oberhalb emer krtttschen Strom&&e durch eme drffustonskontrolherte Verarmung an geldstem Alumrmumoxyd, gefolgt vom Anodeneffekt, ltmtttert. In Scbmelzeu mtt wemger als 1 Gew % Al,O, 1st der Ausdruck i , +/\/I? fur Transtttonw&n 7 xwtchen 8 und 0,l ms konstant. Gehah an Al,O, mehr als 2 Gew %, so nrmmt I Retr> der &\/C nut stergender Stromdrchte fur Transttronszetten xwrschen ca 8 und 1 ms linear ab und erretcht her ktbxeren Zerten emen konstanten Wert. Die Ursaehe ftt dteses Verbalten schemt m emer vorgti mumoxyds zu begen Fiir dte Gleichgewtchtskonstante pi tgen, laugsameu Drssoztatron des Alumtteser Reaktton fand man emen Wert von 0,60; dte Geschwmdigkeitskonstanteu der Vor-und Rtlckreaktron betrugeu 1400 bzw. 2400 s-r. Der Dtffustouskoetlizzent des gel&ten Alummmmoxyds betragt bet 1020°C 1,5 x 1O-6 cmx/s Rer Strom&chten unterhalb 15 A/cm\ 1st dte theorettsche Potenttal/Zettbextehung fur nrverstble Reakttonen effiilt, oberhalb dieses Wertes stelgt das Potential rascher an
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The anode gas evolved during anode etIbct (AE) in NasAlF,-AlsO3 melts consists essentiahy of CO, CO, and CFI. The gas composition was found to be very sensitive to the ahunina concentration and to the AE voltage. In laboratory cells the CF, content ranged from 80 % in putSed cryolite to less than 1%
When a constant cathodic current is applied to an aluminium electrode in a Na3A1F6-AlaO, melt at lOlO"C, the potential decreases gradually and linearly with the square root of time to more negative values. Pronounced potential oscillations occurred at cds above 2A/cm2 and the evolution of sodium gas