Thermochemistry is not a lower bound to the activation energy of endothermic reactions: A kinetic study of the gas-phase reaction of atomic chlorine with ammonia

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Article on a kinetic study of the gas-phase reaction of atomic chlorine with ammonia.

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7 p.

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Gao, Yide; Alecu, I. M.; Hsieh, P-C; Morgan, Brad P.; Marshall, Paul & Krasnoperov, Lev N. March 9, 2006.

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Article on a kinetic study of the gas-phase reaction of atomic chlorine with ammonia.

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7 p.

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Abstract: The rate constant for Cl + NH3 → HCl + NH2 has been measured over 290−570 K by the time-resolved resonance fluorescence technique. Ground-state Cl atoms were generated by 193 nm excimer laser photolysis of CCl4 and reacted under pseudo-first-order conditions with excess NH3. The forward rate constant was fit by the expression k1 = (1.08 ± 0.05) × 10-11 exp(−11.47 ± 0.16 kJ mol-1/RT) cm3 molecule-1 s-1, where the uncertainties in the Arrhenius parameters are ±1 σ and the 95% confidence limits for k1 are ±11%. To rationalize the activation energy, which is 7.4 kJ mol-1 below the endothermicity in the middle of the 1/T range, the potential energy surface was characterized with MPWB1K/6-31++G(2df,2p) theory. The products NH2 + HCl form a hydrogen-bonded adduct, separated from Cl + NH3 by a transition state lower in energy than the products. The rate constant for the reverse process k-1 was derived via modified transition state theory, and the computed k-1 exhibits a negative activation energy, which in combination with the experimental equilibrium constant yields k1 in fair accord with experiment.

Reprinted with permission from the Journal of Physical Chemistry A. Copyright 2006 American Chemical Society.

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  • Journal of Physical Chemistry A, 110(21), American Chemical Society, March 9, 2006, pp. 1-7

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  • Publication Title: Journal of Physical Chemistry A
  • Volume: 110
  • Issue: 21
  • Page Start: 6844
  • Page End: 6850
  • Peer Reviewed: Yes

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  • March 9, 2006

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Gao, Yide; Alecu, I. M.; Hsieh, P-C; Morgan, Brad P.; Marshall, Paul & Krasnoperov, Lev N. Thermochemistry is not a lower bound to the activation energy of endothermic reactions: A kinetic study of the gas-phase reaction of atomic chlorine with ammonia, article, March 9, 2006; [Washington, D.C.]. (https://digital.library.unt.edu/ark:/67531/metadc501422/: accessed April 23, 2024), University of North Texas Libraries, UNT Digital Library, https://digital.library.unt.edu; crediting UNT College of Arts and Sciences.

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