Activation energy for the disproportionation of HBrO2 and estimated heats of formation of HBrO2 and BrO2

The kinetics of the reaction HBrO(2) + HBrO(2) --> HOBr + BrO(3)(-) + H(+) is investigated in aqueous HClO(4) (0.04-0.9 M) and H(2)SO(4) (0.3-0.9 M) media and at temperatures in the range 15-38 degrees C. The reaction is found to be cleanly second order in HBrO(2)], with the experimental rate constant having the form k(exp) = k + k'H(+)]. The half-life of the reaction is on the order of a few tenths of a second in the range 0.01 M < HBrO(2)](0) < 0.02 M. The detailed mechanism of this reaction is discussed. The activation parameters for kare found to be E(double dagger) = 19.0 +/- 0.9 kJ/mol and DeltaS(double dagger) = -132 +/- 3 J/(K mol) in HClO(4), and E(double dagger) = 23.0 +/- 0.5 kJ/mol and DeltaS(double dagger) = -119 +/- 1 J/(K mol) in H(2)SO(4). The activation parameters for k' are found to be E(double dagger) = 25.8 +/- 0.5 kJ/mol and DeltaS(double dagger) = -106 +/- 1 J/(K mol) in HClO(4), and E(double dagger) = 18 +/- 3 kJ/mol and DeltaS(double dagger) = -130 +/- 11 J/(K mol) in H(2)SO(4). The values Delta(f)H(29)(8)(0)BrO(2)(aq)] = 157 kJ/mol and Delta(f)H(29)(8)(0)HBrO(2)(aq)] = -33 kJ/mol are estimated using a trend analysis (bond strengths) based on the assumption Delta(f)H(29)(8)(0)HBrO(2)(aq)] lies between Delta(f)H(29)(8)(0)HOBr(aq)] and Delta(f)H(29)(8)(0)HBrO(3)(aq)] as Delta(f)H(29)(8)(0)HClO(2)(aq)] lies between Delta(f)H(29)(8)(0)HOCl(aq)] and Delta(f)H(29)(8)(0)HClO(3)(aq)]. The estimated value of Delta(f)H(29)(8)(0)BrO(2)(aq)] agrees well with calculated gas-phase values, but the estimated value of Delta(f)H(29)(8)(0)HBrO(2)(aq)], as well as the tabulated value of Delta(f)H(29)(8)(0)HClO(2)(aq)], is in substantial disagreement with calculated gas-phase values. Values of Delta(r)H(0) are estimated for various reactions involving BrO(2) or HBrO(2).