FLUOROGERMANIUM(IV) SALTS OF GRAPHITE -- A SYSTEM IN EQUILIBRIUM WITH ELEMENTAL FLUORINE

Journal Article · Fri Feb 01 04:00:00 EST 1980 · Journal of the Chemical Society, Chemical Communications

DOI:https://doi.org/10.1039/c39800000890· OSTI ID:1048243

McCarron, E M; Grannec, Y J; Bartlett, N

Pyrolytic graphite is not intercalated by GeF{sub 4} alone but is intercalated by GeF{sub 4}/F{sub 2} mixtures to yield, at the intercalation limit, at 20{sup o}, a first-stage material, C{sub 12}GeF{sub 5-6}, which is in equilibrium with gaseous fluorine. GERMANIUM tetrafluoride is a superior fluoride ion acceptor since it can stabilize the O{sub 2}{sup +} ion and the NF{sub 4}{sup +} ion in salts. It is this superior fluoride-ion acceptor capability which must account for our observation that pyrolytic graphite readily intercalates GeF{sub 4} in the presence of fluorine, but does not do so, even with high pressures of GeF{sub 4}, if fluorine is absent, Similar experiments, in which SiF{sub 4} was substituted for GeF{sub 4}, failed to bring about any silicon fluoride intercalation. It has long been known that GeF{sub 4} is a superior fluoride ion acceptor to SiF{sub 4} since, with SF{sub 4}, the former yields the salt (SF{sub 3}{sup +}){sub 2}GeF{sub 6}{sup 2-}, whereas the silicon analogue is not stable at ordinary temperatures and pressures (in spite of the lattice energy of the silicon analogue being slightly more favorable by virtue of the smaller size of SiF{sub 6}{sup 2-}).

• Research Organization: Ernest Orlando Lawrence Berkeley National Laboratory, Berkeley, CA (US)
• Sponsoring Organization: Materials Sciences Division
• DOE Contract Number: AC02-05CH11231
• OSTI ID: 1048243
• Report Number(s): LBL-10228
• Journal Information: Journal of the Chemical Society, Chemical Communications, Journal Name: Journal of the Chemical Society, Chemical Communications Journal Issue: 19 Vol. 1980; ISSN 0022-4936; ISSN JCCCAT
• Country of Publication: United States
• Language: English

Related Subjects

99 GENERAL AND MISCELLANEOUS
CLATHRATES
FLUORIDES
FLUORINE
GERMANIUM
GRAPHITE
MIXTURES
SILICON
SILICON FLUORIDES