Polarographic behaviour of diisopropylaminoethane thiol hydrochloride

The polarographic behaviour of diisopropylaminoethanethiol HCl (RSH) has been studied in presence of 0·1 M LiCl at the dme. The effects of pH, supporting electrolyte, concentration, drop time and temperature on the characteristics of the wave have been investigated. The curves consist of two waves—a small pre-wave followed by a normal anodic wave over the entire pH range (2·60–12·60). The maximum number of moles absorbed on unit area is 3·98 × 10^?10 mole/cm², ie 2·4 × 10¹⁴ molecules/cm², which corresponds to an area 41·6 Ų per adsorbed molecule. The adsorption coefficient and molar adsorption energy are 6·34 × 10² and 26·34 kcal/mole respectively. The electrode reaction is reversible, diffusion-controlled and involves a one-electron tranfer process. The pK of the ?SH group is 10·6. Controlled-potential electrolysis, interaction with mercuric chloride and mathematical analysis reveal the depolarization of mercury with the formation of a Hg(I) complex, mercurous mercaptide RSHg, which rapidly changes to more stable mercuric complex (RS)₂Hg.