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We have used the same estimate (3) of ktrH/ ktrD for all transfers of H./D. from carbon-centered radicals back to Cr. because the radicals in question are similar (tertiary) and none of the equations for S is very sensitive to this isotope effect see text
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. because the radicals in question are similar (tertiary) and none of the equations for S is very sensitive to this isotope effect (see text).
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25
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E-7 is 1.38 kcal/mol more stable than Z-7: J. Franz, Pacific Northwest National Laboratories, personal communication.
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E-7 is 1.38 kcal/mol more stable than Z-7: J. Franz, Pacific Northwest National Laboratories, personal communication.
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26
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It has been suggested8 that such inverse isotope effects are the consequence of a two-step mechanism for H. transfer, with a fast H. transfer equilibrium inside a solvent cage followed by slow diffusion out of the cage
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. transfer equilibrium inside a solvent cage followed by slow diffusion out of the cage.
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27
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33846144602
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The effect of the temperature difference is insignificant compared to the uncertainty in our rate constants
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The effect of the temperature difference is insignificant compared to the uncertainty in our rate constants.
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Decrease of deuterium content in 4-d5 was observed under prolonged reaction times or at high temperatures
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5 was observed under prolonged reaction times or at high temperatures.
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43
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33846172176
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2H is approximately 0.01 M.
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2H is approximately 0.01 M.
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