Measurement of association and dissociation rate constants for lead(II)/18-crown-6 using square wave voltammetry at a glassy carbon mercury film electrode

Understanding the rate parameters of metal ion-ligand complexes is necessary for sensing, separations, and responsive materials. The complexation between 18-crown-6 and lead(II) is of particular interest due to the potential use of this chemistry in sensors and separations. We have applied square wave voltammetry at a glassy carbon mercury film electrode to this problem. Lead(II) in aqueous solution containing an excess of 18-crown-6, studied with different experimental time scales, yields stoichiometry, binding constants, and rate constants (25 degrees C). For pulse times longer than 10 ms, the glassy carbon mercury film electrode acts as a planar electrode. For shorter pulse times, a roughness correction factor must be used to calculate dimensionless current because of the increase in effective area due to the droplike nature of the adsorbed mercury. Lead(II) forms a 1:1 complex with 18-crown-6 in both nitrate and perchlorate media. Log K for the complex with the nitrate counterion is 4.13 +/- 0.09 (SEM); in the presence of perchlorate it is 4.35 +/- 0.09 (SEM). The formation rate constants, kf, for the nitrate and perchlorate systems are (3.82 +/- 0.89) x 107 and (5.92 +/- 1.97) x 106 M-1 s-1, respectively. The dissociation rate constants, kd, are (2.83 +/- 0.66) x 103 s-1 with nitrate as the counterion and (2.64 +/- 0.88) x 102 s-1 with perchlorate as the counterion. The significant difference in rate constants for the two anions is probably caused by the ion pairing that occurs with lead(II) nitrate.