Ab initio MO calculations and experimental observations on the reactivities of elemental fluorine and chlorine with graphite in the presence of HF

Fujio Okino, Hideki Tanaka, Pascal Lagassie, Shigeaki Suganuma, Hidekazu Touhara

Research output: Contribution to journalArticle

2 Citations (Scopus)

Abstract

Ab initio MO calculations have been carried out on F2 HF and Cl2 HF complexes in order to shed light on the reactivities of elemental fluorine and chlorine with graphite. The results show that the F2 HF and Cl2 HF complexes are stabilized by 10.50 and 5.2kJ/mol respectively. A partial charge transfer from the halogen molecules (X2) to HF occurs. The X2 molecules are polarized and the X atoms which are not hydrogen-bonded to HF carry a partial positive charge, making the complexes suitable for the dipole-induced dipole interaction with graphite. Furthermore, the X2 molecules interacting with HF can be regarded as easily polarizable, large "soft oxidants", facilitating the subsequent charge transfer from graphite. HF plays a catalytic role both in intercalation and deintercalation processes. In contrast with fluorine, the reaction of chlorine with graphite in the presence of liquid HF barely yielded a stage-two compound after a prolonged reaction time, which was in agreement with the results of calculation. The lower reactivity of chlorine is attributed to the weaker interaction of Cl2 with HF and its smaller oxidizing ability.

Original languageEnglish
Pages (from-to)45-52
Number of pages8
JournalJournal of Fluorine Chemistry
Volume57
Issue number1-3
DOIs
Publication statusPublished - Jan 1 1992
Externally publishedYes

ASJC Scopus subject areas

  • Biochemistry
  • Environmental Chemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

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