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Volumn 14, Issue 19, 1998, Pages

A new approach for measuring the effect of a monolayer on molecular transfer across an air/water interface using scanning electrochemical microscopy

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EID: 11644293532     PISSN: 07437463     EISSN: None     Source Type: Journal    
DOI: None     Document Type: Article
Times cited : (3)

References (58)
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    • A 25 μm diameter Ag or Ptsubmarine electrode was used: Slevin, C. J.; Macpherson, J. V.; Unwin, P. R. J. Phys. Chem. B 1997, 101, 10851. The two types of electrodes yielded similar results. All data reported herein were obtained with an Ag UME.
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    • note
    • All measurements were mode in a two-electrode arrangement with a silver wire operating as a quasi-reference electrode (AgQRE). The UME and AgQRE were positioned in the well section of the Langmuir trough.
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    • note
    • 3 (AR Grade, Fisons, Loughborough, U.K.). All aqueous solutions used distilled water pumped through an Elgastat Spectrum A deionizer (resistivity ≥ 18 MQ cm, The Elga Group, High Wycombe, U.K.).
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    • 196 The Ag UME was biased at the limiting potential for oxygen reduction, determined by voltammetry as -0.88 V vs AgQRE. All measurements were made at ambient temperature (20 ± 1 °C).
  • 51
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    • This was used as the distance of closest approach for subsequent approach curve measurements The distance was confirmed with independent measurements of ferrocyanide oxidation, for the range of monolayer compressions of interest. Approach curves followed the theory for hindered diffusion (Kwak, J.; Bard, A. J. Anal. Chem. 1989, 61, 1221), with a consistent distance of closest approach.
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    • 2. Identical results were obtained with compression at half this speed.
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    • Zaitsev, S. Y.; Kalmer, U.; Möbius, D. Colloids Surf., A 1995, 94, 137. Effectively identical isotherms were obtained with and without the probe UME, indicating that the latter was nonperturbing.
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    • note
    • After the pressure was adjusted, the system was allowed to settle for 2 min before approach curves were recorded, π-time and A-time data were recorded simultaneously during approach curves to ensure that the monolayer was stable during local electrochemical measurements. No contamination of the electrode surface was observed between successive approach curve measurements as evidenced by consistent i(∞) values.


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