KINETICS OF HYDROLYSIS OF cis-DIFLUORO-BIS-(ETHYLENEDIAMINE)-CHROMIUM(III) CATION

Journal Article · Mon Mar 20 04:00:00 EST 1961 · Journal of the American Chemical Society (U.S.)

DOI:https://doi.org/10.1021/ja01467a004· OSTI ID:4067048

Fehrmann, K R.A.; Garner, C S

The rates of release of fiuoride by acid and base hydrolysis of cis- STACr(en)/sub 2/F/sub 2/!/sup +/ were determined over a range of pH 1 to 8. At 25 deg the pseudo first-order aquation rate constant for loss of the first fiuoride in 0.1 f HClO/sub 4/ is 5.3 x 10/sup -6/ sec/sup -1/, much less than the corresponding rate constants of cis-STACo(en)/sub 2/F/sub 2/!/sup +/ and cis- STACr(en)/sub 2/Cl/sub 2/!/sup +/ in 0.1 f HNO/sub 3/ . The Arrhenius activation energy is 23 plus or minus 1 kcal./mole. The aquation of cis-STACr(en)/sub 2/F/ sub 2/!/sup +/ is acid catalyzed like the cobalt analog but, unlike the dichloro cobalt and chromium analogs, presumably because the difiuoro complexes aquate by a mechanism involving an intermediate reactive protonated complex. Cation- exchange and spectral evidence indicate that the aquation product is largely, if not entirely, cisSTACr(en)/sub 2/(H/sub 2/O)F!/sup 2+/. Fluoride is taken up by one or more reaction products in later stages of the hydrolysis. The aquation appears not to be accelerated by visible light. (auth)

• Research Organization: Univ. of California, Los Angeles
• Sponsoring Organization: USDOE
• NSA Number: NSA-15-014198
• OSTI ID: 4067048
• Journal Information: Journal of the American Chemical Society (U.S.), Journal Name: Journal of the American Chemical Society (U.S.) Vol. Vol: 83; ISSN JACSA
• Country of Publication: Country unknown/Code not available
• Language: English

Related Subjects

CATALYSIS
CATIONS
CHEMISTRY
CHROMIUM COMPOUNDS
COBALT COMPOUNDS
COMPLEXES
DECOMPOSITION
FLUORIDES
ION EXCHANGE
LIGHT
ORGANIC COMPOUNDS
WATER