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Calorimetrically measurable enthalpic isotope effect.

Kent Ballard1, Richard C Reiter, Cheryl D Stevenson

  • 1Department of Chemistry, Illinois State University, Normal, IL 61790-4160, USA.

The Journal of Physical Chemistry. A
|December 22, 2006
PubMed
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The reaction of perdeuterated naphthalene anion radicals with water is more exothermic than the perprotiated system. This suggests that perdeuteration decreases the heat of naphthalene hydrogenation.

Area of Science:

  • Physical Chemistry
  • Chemical Thermodynamics
  • Isotope Effects

Background:

  • Naphthalene and its anion radical are important in organic chemistry.
  • Isotope effects on chemical reactions can provide insights into reaction mechanisms.
  • Calorimetric studies are crucial for determining reaction enthalpies.

Purpose of the Study:

  • To investigate the effect of deuterium substitution on the enthalpy of reaction of the naphthalene anion radical with water.
  • To determine the impact of perdeuteration on the heat of hydrogenation of naphthalene.

Main Methods:

  • Calorimetric measurements were used to determine the enthalpy of reaction.
  • The study compared the reaction of perdeuterated naphthalene anion radical with water to the perprotiated system.

Related Experiment Videos

  • Enthalpy of electron transfer between naphthalene and its perdeuterated analogue was considered.

    • Main Results:

    • The reaction of the perdeuterated naphthalene anion radical with water was found to be more exothermic by approximately 2.2 kcal/mol compared to the perprotiated system.
    • The heat of hydrogenation of naphthalene was calculated to decrease by about 1.8 kcal/mol upon perdeuteration.

    Conclusions:

    • Perdeuteration of naphthalene leads to a more exothermic reaction with water for its anion radical.
    • The observed isotope effect indicates a significant influence of deuterium on the thermodynamics of naphthalene hydrogenation.