Heat of formation of the hydroperoxyl radical HOO via negative ion studies

Ramond, T. M., Blanksby, Stephen J., Kato, S., Bierbaum, V. M., Davico, G. E., Schwartz, R. L., Lineberger, W. C., & Ellison, G. B. (2002) Heat of formation of the hydroperoxyl radical HOO via negative ion studies. Journal of Physical Chemistry A, 106(42), pp. 9641-9647.

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We present a determination of Delta(f)H(298)(HOO) based upon a negative. ion thermodynamic cycle. The photoelectron spectra of HOO- and DOO- were used to measure the molecular electron affinities (EAs). In a separate experiment, a tandem flowing afterglow-selected ion flow tube (FA-SIFT) was used to measure the forward and reverse rate constants for HOO- + HCdropCH reversible arrow HOOH + HCdropC(-) at 298 K, which gave a value for Delta(acid)H(298)(HOO-H). The experiments yield the following values: EA(HOO) = 1.078 +/- 0.006 eV; T-0((X) over tilde HOO - (A) over tilde HOO) = 0.872 +/- 0.007 eV; EA(DOO) = 1.077 +/- 0.005 eV; T-0((X) over tilde DOO - (A) over tilde DOO) = 0.874 +/- 0.007 eV; Delta(acid)G(298)(HOO-H) = 369.5 +/- 0.4 kcal mol(-1); and Delta(acid)H(298)(HOO-H) = 376.5 +/- 0.4 kcal mol(-1). The acidity/EA thermochemical cycle yields values for the bond enthalpies of DH298(HOO-H) = 87.8 +/- 0.5 kcal mol(-1) and Do(HOO-H) = 86.6 +/- 0.5 kcal mol(-1). We recommend the following values for the heats of formation of the hydroperoxyl radical: Delta(f)H(298)(HOO) = 3.2 +/- 0.5 kcal mol(-1) and Delta(f)H(0)(HOO) = 3.9 +/- 0.5 kcal mol(-1); we recommend that these values supersede those listed in the current NIST-JANAF thermochemical tables.

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55 citations in Web of Science®
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ID Code: 71515
Item Type: Journal Article
Refereed: Yes
Additional URLs:
Keywords: gas-phase acidity, photoelectron-spectroscopy, electron-affinity, hydrogen-peroxide, thermochemistry, photodetachment, chemistry, spectrum, h2o2, oh
DOI: 10.1021/jp014614h
ISSN: 1520-5215 (online ) 1089-5639 (print)
Divisions: Current > QUT Faculties and Divisions > Science & Engineering Faculty
Copyright Owner: Copyright 2002 American Chemical Society
Deposited On: 13 May 2014 04:14
Last Modified: 21 Jun 2017 08:01

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