Re-evaluation of Sn(II)-Br− Speciation in Concentrated Bromide Media by Cyclic Voltammetry
- Authors
- Park, D; Chang, Jinho
- Issue Date
- Jun-2016
- Publisher
- WILEY-V C H VERLAG GMBH
- Keywords
- Sn(II)-Br- speciation; Sn(II)Br-7(5-); Sn(II)Br-8(6-); cyclic voltammetry
- Citation
- ELECTROANALYSIS, v.28, no.6, pp.1356 - 1361
- Indexed
- SCIE
SCOPUS
- Journal Title
- ELECTROANALYSIS
- Volume
- 28
- Number
- 6
- Start Page
- 1356
- End Page
- 1361
- URI
- https://scholarworks.bwise.kr/hanyang/handle/2021.sw.hanyang/154398
- DOI
- 10.1002/elan.201500629
- ISSN
- 1040-0397
- Abstract
- We report re-evaluated Sn(II)-Br- speciation by cyclic voltammetry on a glassy carbon (GC) electrode in concentrated Br- aqueous solutions. Contrary to the previous reports, electrochemical evidences of Sn(II)Br-5(3-), Sn(II)Br-6(4-), Sn(II)Br-7(5-), and Sn(II)Br-8(6-) were found in aqueous solutions containing different Br- concentrations with ionic strength, I=6. Formation constants (j) of Sn(II)-Br- speciation reactions and corresponding fractions of Sn(II)Br(j)(2-j)f(j) were evaluated. Compared to f(j) as a function of Br- concentrations based on the previous report by Fedorov etal., f(j) measured by our electrochemical measurements were dramatically different. In an aqueous solution with 6M Br-, 50% of Sn(II)Br-8(6-), 20% of each Sn(II)Br-6(4-) and Sn(II)Br-7(5-) exist in total Sn(II)-Br-. The diffusion coefficients, D of Sn(II)-Br- in aqueous solutions containing different Br- concentrations were estimated, and D decreased as a Br- concentration in the solution increased, which is mainly attributed to the enlarged molecular size of Sn(II)-Br- with more Br- coordination. A nucleation mechanism was also studied as a function of Sn(II)-Br- speciation. It was found that the nucleation mechanism of an electrodeposited Sn on a GC electrode gradually changed from instantaneous to progressive as j in Sn(II)Br-j(2-j) increases to 8, indicating the electrochemical Sn nucleation on a GC electrode is strongly dependent on Sn(II)-Br- speciation.
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