A preliminary examination of the electrochemical oxidation of n-butanethiolate monolayers on polycrystalline gold electrodes was undertaken in order to ascertain the possible identities of the resulting oxidation products. These studies are an outgrowth of our efforts to develop a method using electrospray ionization mass spectrometry to quantitatively characterize the composition of mixed alkanethiol self-assembled monolayers. Cyclic voltammetric scan rate studies have indicated that oxidation of these films is incomplete at fast scan rates(>10 mV/s), consistent with the notion that oxidative desorption is kinetically limited. In addition, chronocoulometric studies have indicated that the average oxidative:reductive charge density ratio = 10.2. This ratio greatly exceeds that expected for formation of either butylsulfinate (CH3(CH2)3SO2�, 3 e�-process) or butylsulfonate (CH3(CH2)3SO3�, 5 e�-process), suggesting that oxidation of the a-carbon on the alkyl chain may occur as well.

Examination of the oxidative desorption of n-butanethiolate monolayers on polycrystalline gold electrodes by cyclic voltammetry and coulometry

245th National Meeting (2013)

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