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Degenerate conversion

An intramolecular rearrangement with 1,2-shifts of the hydrogen between nonequivalent positions is the degenerate conversion of the 2,3,5,6-tetramethylbenzenium... [Pg.145]

The parameter A reflects the intrinsic reaction barrier . It coincides with the free activation energy for degenerate conversions (A = AG at AG° = 0). If the quadratic term in the Marcus equation is neglected it takes the form... [Pg.168]

For these conditions the product distribution is time independent when the overall reaction orders are identical. However, when (mj + wx) > (m2 + n2 the product distribution changes as time proceeds with the ratio of the product formed by reaction 1 to that formed by reaction 2, declining as the reaction proceeds. Conversely, if (m2 + n2) > (mx + nx), this ratio will increase. Experiments of this type can provide extremely useful clues as to the form of the reaction rate expression and as to the type of experiments that should be performed next. Another technique that is often useful in studies of these systems is the use of a large excess of one reactant so as to cause a degeneration of the concentration dependent term to a simpler form. [Pg.146]

See other pages where Degenerate conversion is mentioned: [Pg.35]    [Pg.58]    [Pg.35]    [Pg.182]    [Pg.163]    [Pg.172]    [Pg.252]    [Pg.35]    [Pg.58]    [Pg.35]    [Pg.182]    [Pg.163]    [Pg.172]    [Pg.252]    [Pg.561]    [Pg.588]    [Pg.599]    [Pg.286]    [Pg.48]    [Pg.163]    [Pg.94]    [Pg.114]    [Pg.303]    [Pg.307]    [Pg.254]    [Pg.478]    [Pg.669]    [Pg.696]    [Pg.707]    [Pg.89]    [Pg.661]    [Pg.733]    [Pg.227]    [Pg.234]    [Pg.264]    [Pg.772]    [Pg.773]    [Pg.784]    [Pg.177]    [Pg.331]    [Pg.147]    [Pg.50]    [Pg.29]    [Pg.65]    [Pg.72]    [Pg.87]    [Pg.131]    [Pg.146]    [Pg.148]    [Pg.169]    [Pg.171]    [Pg.172]   


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