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4.
Mechanistic Study of Ir(III) and Hg(II) Co-Catalyzed Oxidation of
Mannitol by an Alkaline N-Bromosuccinnimide
Sheila Srivastava*, Anju Singh and Saumya Bajpai ,Tushar Bajpai
Chemical Laboratories, Feroze Gandhi College, Raebareli – 229001,
U.P., India.
E-mail:
she_ila72@yahoo.com
/
saumya.90@rediffmail.com
Abstract.
The kinetics of Ir(III) catalyzed oxidation of Mannitol in
an alkaline medium by N- Bromosuccinnimide has been studied
in the temperature range 30-450 C. The reaction was carried
out in the presence of mercuric acetate which co-catalyzes
the reaction and the reaction rate follows a fractional
positive order with respect to it. First order kinetics has
been depicted in case of catalyst Iridium(III) chloride. The
rate showed fractional positive kinetics with respect to the
oxidant as well as [OH-] and [Cl-].
Variation in the concentration of Mannitol showed negligible
impact on the reaction rate implying zero order with respect
to substrate. Various activation parameters have been
calculated. A suitable mechanism in agreement with observed
kinetics has been proposed.
KEY WORDS:
oxidation; catalyst; mannitol; NBS; Iridium(III).
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