Rotating Disk Electrode -a hydrodynamic method

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1 Rotatng Dsk Electode -a hdodnamc method Fe Lu Ma 3, 0 ente fo Electochemcal Engneeng Reseach Depatment of hemcal and Bomolecula Engneeng

2 Rotatng Dsk Electode A otatng dsk electode RDE s a hdodnamc wokng electode used n a thee electode sstem. The RDE s one of the few convectve electode sstems fo whch the hdodnamc equatons and the convectve-dffuson equaton have been solved goousl fo the stead state. ente fo Electochemcal Engneeng Reseach, ho Unvest

3 onstuct of RDE Shaft bass Insulato Teflon Bush contact Dsk RDE Rotatng Dsk Electode RDE s constucted fom a dsk of electode mateal mbedded n a od of nsulatng mateal. The electode s attached to a moto and otated at a cetan fequenc. Insulatng mateal : Teflon, epox esn o othe plastc []. Bottom Vew ente fo Electochemcal Engneeng Reseach, ho Unvest 3

4 Veloct Pofle At Dsk Suface, 0, v 0, 0 and v. The soluton s dagged along at the suface of the dsk at the angula veloct ω. In the bulk soluton, v 0, v 0 and v U 0. Fo electochemcal studes, the mpotant veloct s v and v, Nea the suface of the otatng dsk 0, these veloctes ae gven b: 3/ / v 0.5 3/ / v 0.5 Fo, the lmt veloct n decton, / U 0 s: U lm v Hdodnamc bounda lae thckness / 3.6, v 0.8U 0, h 3.6 / ente fo Electochemcal Engneeng Reseach, ho Unvest v 0 h / 4 At

5 ente fo Electochemcal Engneeng Reseach, ho Unvest onvectve-dffuson Equaton 5 Stead-state convectve-dffuson equaton n tems of clndcal coodnates: Lmt cuent condton: Substtuton of the value of : D v v v dffuson convecton D v v / 3/.5 0 v

6 Soluton of onvectve-dffuson Equaton 0.5 Bounda condton: uent s the flux at the electode suface, that s: Unde lmt condtons: 3/ / Soluton of convectve-dffuson equaton: 0 0 nfad l, c l, c 6 D 0 /3 / /6 0. nfad ente fo Electochemcal Engneeng Reseach, ho Unvest 6

7 Dffuson Lae Thckness Levch equaton: Fo smple stead-state dffuson lae model: Fo RDE: l, c 6 /3 / /6 0. nfad D l, c nfam nfa m D 0.6D /3 / / 6 /3 / /6.6D ente fo Electochemcal Engneeng Reseach, ho Unvest 7

8 ente fo Electochemcal Engneeng Reseach, ho Unvest Geneal uent-potental uves at RDE 8 Bounda condton: uent s the flux at the electode suface, that s: Soluton of convectve-dffuson equaton: ombne wth Levch equaton: D nfad 0] [ 0.6 /6 / /3 nfad 0, c l

9 Kouteck-Levch Equaton Fo Levch equaton, s popotonal to / l c. A devaton of a / plot of vs. fom a staght lne ntesectng the ognal suggest a knetc lmtaton s nvolved n the electon-tansfe eacton. Fo totall vesble one-step one-electon eacton, the dsk cuent s : E 0 Whee : E s fowad eacton ate at E. k f, FAk FAk f f E l, c Wth eaangement and defnng: K FAk Kouteck-Levch equaton: K l, c K 0. 6nFAD f E /3 ente fo Electochemcal Engneeng Reseach, ho Unvest / / 6 9

10 Kouteck-Levch Equaton K l, c K 0. 6nFAD /3 / / 6 Vaaton of і wth ω / at an RDE fo an electode eacton wth slow knetcs ente fo Electochemcal Engneeng Reseach, ho Unvest 0

11 Advantages of RDE A stead state s attaned athe quckl and measuements can be made wth hgh pecson at RDE []. RDE gves good epoducblt and stable polazaton cuve. In stagnant soluton, dffuson lae thckness s the same as bounda lae thckness, t s eas to be dstub b extenal dstubance. But fo RDE: h D / The dffuson lae thckness s fa less than bounda lae thckness, the dffuson lae s potect b bounda lae whch makes the polazaton cuve stable and has good epoducblt. [] L.H. Mendoza-Huza,.H. Ros Rees, M. Rvea and.a. Galán-Vdal, A Voltammetc Stud f The Undepotental Deposton f obalt nto A Glass abon Electode, AZojomo ISSN 833-X Volume 3 Janua 007 ente fo Electochemcal Engneeng Reseach, ho Unvest

12 Applcatons of RDE I. Measue Fe + /Fe 3+ oncentatons Fom the Levch equaton, Levch cuent the concentaton: l, c onsde a eacton:, 0.6nFAD a 0.6nFAD Fe 3 /3 /3 / /, s dectl popotonal to f the l c s known, the concentaton of Fe + /Fe 3+ can be calculated b lnea egesson usng the followng model [3] : / 6 / 6 e Fe /3 / l, c 0. 6nFAD l, c a a /6 b [3] Xn Jn, Geadne G. Botte, Electochemcal technque to measue FeII and FeIII concentatons smultaneousl, J Appl Electochem : ente fo Electochemcal Engneeng Reseach, ho Unvest

13 Applcatons of RDE II. Detemne Dffuson oeffcent Levch equaton: l, c 6 /3 / /6 0. nfad Plottng і l,s vs. ω / elds staght lne wth slope: slope /3 /6 0.6nFAD Dffuson coeffcent can be calculated b: Plots of і l,s vs ω /. Wokng soluton: K 3 FeN 6 0 mm + K 4 FeN 6 0 mm n Na S40. M at a vteous cabon RDE. D Slope / nfa 3 ente fo Electochemcal Engneeng Reseach, ho Unvest 3

14 / Applcaton fo cuent eseach III. Detemne knetc paametes =.07x Kouteck-Levch equaton: / K K 0.6nFAD /3 / / / K s the ntecept at axs. ω -/ Plots of і - vs ω /. Wokng soluton: 0.33 M Uea and 5 M KH wth N base RDE at 0.5V. ente fo Electochemcal Engneeng Reseach, ho Unvest 4

15 Thank You! ente fo Electochemcal Engneeng Reseach, ho Unvest 5

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