Heterolytic (R-H)+·Bond Dissociation Free Energies in Solution Derived from Electrochemically-monitored Acid-Base Titration(EABT)

Abstract

Abstract: An Electrochemically Monitored Acid Base Titration(EABT) method using cyclic voltammetry was established to measure directly the concentration change of all species, then to get the acidic dissociation constants(pK_RH^+· ) and bond heterolysis energies(Δ Ghet ) of radical cations. pK_RH^+· s of phenothiazine and its analogues in dimethylsulfoxide and acetonitrile were obtained and in good accordance with the pK_RH^+· s derived from indirect methods. So, the credence of the present method was tested. Because the exact values of p Ka(or BDE) of the parent molecules and of the anion oxidation potentials needed by indirect methods are not required, the EABTmethod can be applicable to a wide range oforganic systems whose pK_RH^+· s may otherwise be difficult to be obtained.

Key words: pK_RH^+·, Radical cation, Cyclic voltammetry, Bond heterolysis energy

CLC Number:

O621.16

TrendMD:

ZENG Qing, HE Jia-Qi, CHENG Jin-Pei . Heterolytic (R-H)^+·Bond Dissociation Free Energies in Solution Derived from Electrochemically-monitored Acid-Base Titration(EABT)[J]. Chem. J. Chinese Universities, 2002, 23(7): 1285.

References

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