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-1) was present as co-adsorbate in both the aqueous electrode-coating solution and the cryosolvent cell solution (usually 70% v/v methanol; Prolabo > 99%) with 0.1 M NaCl buffered by HEPES at pH* 7.4 or acetate at pH* 5.0. The aqueous saturated calomel reference electrode (SCE) with internal salt bridge was held in a Luggin side arm filled with cryosolvent but maintained at room temperature with a water jacket. Values of pH and pH* [see: ref. 3(a), and R. G. Bates, Determination of pH: Theory and Practice, Wiley, New York, 1973] were measured with glass pH electrode at 273 K, without corrections. Cell anaerobicity was maintained by purging with Ar. Temperatures were controlled by immersing the cell compartment in a stirred ethanol bath, to which was added dry ice or frozen ethanol, and measured (±1 K) with a thermometer after 10 min equilibration. Background currents were subtracted using an in-house analysis program (Dr H. A. Heering).
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Determination of pH: Theory and Practice
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Bates, R.G.1
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28
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0345237569
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note
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o/ varies trivially as a result of pH* changes. Values obtained were: at 273 K (aqueous) pK = 5.6, at 273 K (70% v/v methanol) pK = 6.7, at 198 K (70% v/v methanol) pK = 6.8 (an apparent value since pH* is measured at 273 K).
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29
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0020828861
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The peak broadening observed as the temperature is lowered is not due to increased uncompensated resistance (iR); like irreversible electrode kinetics, iR effects are associated with large increasaes in peak separation. See: L. Roullier and E. Laviron, J. Electroanal. Interfacial Electrochem., 1983, 157, 193.
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Roullier, L.1
Laviron, E.2
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30
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0345237568
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note
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Peak potentials were completely restored although peak areas were ca. 10% smaller than measured at the start of the experiment.
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