THE MECHANISM OF SUBSTITUTION REACTIONS AT OCTAHEDRAL SITES. III DEUTERIUM ISOTOPE EFFECTS IN THE ACID AND BASE HYDROLYSIS OF ANIONOPENTAAMMINECHROMIUM(III) IONS

Journal Article · Wed Jan 01 04:00:00 EST 1964 · Inorganic Chemistry (U.S.)

DOI:https://doi.org/10.1021/ic50011a031· OSTI ID:4144917

Parris, M; Wallace, W J

The hydrolysis of Cr(NH/sub 3/)/sub 5/X/sup 2+/, where X = Cl/sup -/, Br/ sup /, I/sup -/, and SCN/sup -/, was examined in solvents containing varying proportions of H/sub 2/O and D/sub 2/O. For X = SCN/sup -/, Cl/sup -/, Br/sup -/ , and I/sup -/, k/sub D/, /k/sub H/ takes on the values 0.43, 0.60, 0.95, and 1.51, re spectively. The interpretation of these effects suggests a transition state that intimately involves one or more water molecules and is strongly polar but does not involve separated ions. In basic solution, the corresponding ratio of rate constants for the chloro complex is 1.37. The interpretation of the data suggests that the transition state for the base hydrolysis involves direct interaction and charge transfer between the hydroxide ion and the metal ion. The exchange of hydrogen between the solvent and the ammonia molecules of the solute was also measured. (auth)

• Research Organization: Univ. of Alberta, Edmonton
• Sponsoring Organization: USDOE
• NSA Number: NSA-18-006807
• OSTI ID: 4144917
• Journal Information: Inorganic Chemistry (U.S.), Journal Name: Inorganic Chemistry (U.S.) Vol. Vol: 3; ISSN INOCA
• Country of Publication: Country unknown/Code not available
• Language: English

Related Subjects

ACIDS
AMMONIA
BROMIDES
CHEMICAL REACTIONS
CHEMISTRY
CHLORIDES
CHROMIUM COMPLEXES
CYANATES
DEUTERIUM
ELECTRIC CHARGES
ENERGY LEVELS
HEAVY WATER
HYDROGEN
HYDROLYSIS
HYDROXIDES
INTERACTIONS
IODIDES
IONS
ISOTOPE EFFECTS
MEASURED VALUES
MOLECULES
NUMERICALS
ORGANIC SULFUR COMPOUNDS
SOLUTIONS
SOLVENTS
TRANSIENTS
VARIATIONS
WATER