The Low Energy Unimolecular Reaction Rate Constants for the Gas Phase Ni + Mediated Dissociation of the C-C  -bond in Acetone. NiAc + → NiCO + + C 2 H.

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Presentation transcript:

The Low Energy Unimolecular Reaction Rate Constants for the Gas Phase Ni + Mediated Dissociation of the C-C  -bond in Acetone. NiAc + → NiCO + + C 2 H 6 Vanessa Castleberry and Darrin Bellert, PhD Baylor University

Our Instrument

A Parent Mass Spectrum

Tuning the Hemispherical Energy Analyzer

Scheme

Kinetic Studies

How we make our measurements

How We Interpret the Data

C – C  -bond activation occurs In Acetone photolysis of 2 C-C  - bond * Acetone dissociation catalyzed by Ni + in our studies * Woodbridge, et. al., JPC, 1988, 92(19)

Rate Constants for Different Energies Internal energy (cm -1 ) k(E)(  s -1 ) ± ± ± ± ± 0.003

Which Step is Rate Limiting??

2 Probable Candidates

But, these results can’t reveal which step is rate limiting Comparison studies using the isotope effect: d 6 - Acetone

Kinetic Isotope Effect

Apparent Rate Limiting Step?

Acknowledgements Bellert group: – Ivanna Laboren – Otsmar Villarroel – Jason Dee – Sarah Frey (enthusiastic undergraduate) Baylor University Department of Chemistry and Biochemistry

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