화학공학소재연구정보센터
Inorganic Chemistry, Vol.38, No.23, 5374-5378, 1999
Kinetics and mechanisms of the oxidation of hydrazinium ion (N2H5+) by ICI and IBr; Determination of the protonation constant of N2H5+
The kinetics of N2H5+ oxidation by ICI and IBr in 0.1-1.0 M [H+] is investigated by following the formation of I2Cl- and I2Br- with excess ICl2- and IBr2-, respectively, when total hydrazine is the limiting reactant. Highly acidic solutions are needed to suppress the rates of N2H4 reactions and to avoid hydrolysis of the interhalogens. Protonation constants of N2H5+, K-P2 = [N2H62+]/[N2H5+][H+], measured spectrophotometrically at 25.0 degrees C with picric acid as an indicator, are 1.61 M-1 (mu = 0.50 M) and 1.72 M-1 (mu = 1.00 M). In the proposed mechanisms, ICl and IBr react by an IC transfer process to N2H5+ with loss of H+ (k(1)) to form a steady-state species, IN2H4+, that eliminates I- and H+ to give N2H3+ (k(2)) Subsequent reactions consume a second interhalogen, as diazine (N2H2) is rapidly oxidized to N-2. Rate constants (25.0 degrees C, mu = 1.00 M) for the ICl/N2H5+ reaction are k(1) = 4.12 x 10(6) M-1 s(-1), k(-1)/k(2) = 1.9 M-2 and for the IBr/N2H5+ reaction are k(1) = 7.6 x 10(4) M-1 s(-1), k(-1)/k(2) = 28 M-2 The relative rates of oxidation of N2H5+ are ICl much greater than IBr much greater than I-2.