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 language | English |
|---|---|
| Pages (from-to) | 45-52 |
| Number of pages | 8 |
| Journal | Journal of Fluorine Chemistry |
| Volume | 57 |
| Issue number | 1-3 |
| DOIs | |
| Publication status | Published - 1992 |
| Externally published | Yes |
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ASJC Scopus subject areas
- Inorganic Chemistry
- Organic Chemistry
- Materials Chemistry
- Polymers and Plastics
Cite this
Ab initio MO calculations and experimental observations on the reactivities of elemental fluorine and chlorine with graphite in the presence of HF. / Okino, Fujio; Tanaka, Hideki; Lagassie, Pascal; Suganuma, Shigeaki; Touhara, Hidekazu.
In: Journal of Fluorine Chemistry, Vol. 57, No. 1-3, 1992, p. 45-52.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Ab initio MO calculations and experimental observations on the reactivities of elemental fluorine and chlorine with graphite in the presence of HF
AU - Okino, Fujio
AU - Tanaka, Hideki
AU - Lagassie, Pascal
AU - Suganuma, Shigeaki
AU - Touhara, Hidekazu
PY - 1992
Y1 - 1992
N2 - 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.
AB - 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.
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U2 - 10.1016/S0022-1139(00)82815-8
DO - 10.1016/S0022-1139(00)82815-8
M3 - Article
AN - SCOPUS:44049114637
VL - 57
SP - 45
EP - 52
JO - Journal of Fluorine Chemistry
JF - Journal of Fluorine Chemistry
SN - 0022-1139
IS - 1-3
ER -