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A New Method for Determining the Stoichiometric Number of the Rate-determining Step.：application to the Chlorine Electrode Reaction on Platinum
| Content Provider | Semantic Scholar |
|---|---|
| Author | Enyo, Michio Yokoyama, Takamitsu |
| Copyright Year | 1969 |
| Abstract | A new method for determining the stoichiometric number, )),., of the rate-determining step was developed with special reference to electrode reactions. The method is based on a comparison of the electrode potential-current relations obtained under different conditions, and involves neither an isotope exchange reaction nor an extrapolation of a Tafel line to the reversible potential. The method was applied to the chlorine electrode reaction, 2 CI = CI2 + 2 e, on Pt in 2 N H 2S04 containing HCI at various concentrations. The value of ))r was found to be practically independent of chlorine pressure (1-0.089 atm) and of cr concentration (0.20.006 N), but dependent upon the electrode potential; ))r was found to be two in the potential region more positive than the reversible potential at 1 atm CI2 and 0.2N HCI, and to decrease toward unity upon change of the electrode potential toward more negative values. In the positive potential region, the order of the chlorine evolution reaction was 1.1 ± 0.1 for CIand -0.03 ± 0.05 for C1 2 . In the potential region more negative than -100 m V, that of the chlorine ionization reaction was approximately unity for CI2 and 0 ± 0.05 for CI-. On the basis of these values and the above ))r-values, it was concluded that the chlorine electrode reaction proceeds by the scheme, where CI (a) is the chlorine adatom, and the first determines the rate (the "slow-discharge" mechanism) in the positive region and the second (the "catalytic" mechanism) in the negative region. Introduction The stoichiometric number, J.i,., of the rate-determining step, first introduced by HORIUTI,1,2) is of primary importance in analyzing reaction kinetics and *) The Research Institute for Catalysis, Hokkaido University, Sapporo, Japan. 1 - |
| Starting Page | 1 |
| Ending Page | 13 |
| Page Count | 13 |
| File Format | PDF HTM / HTML |
| Volume Number | 17 |
| Alternate Webpage(s) | https://eprints.lib.hokudai.ac.jp/dspace/bitstream/2115/24886/1/17(1)_P1-13.pdf |
| Language | English |
| Access Restriction | Open |
| Content Type | Text |
| Resource Type | Article |
