Photocalorimetry. 4. Enthalpies of substitution reactions of rhodium(III) and iridium(III) pentaammine halides and of ruthenium(II) hexaammine
Journal Article
·
· J. Phys. Chem.; (United States)
Photocalorimetric enthalpies of aquation at 25 /sup 0/C are reported for Rh(NH/sub 3/)/sub 5/X/sup 2 +/, X = Cl/sup -/, Br/sup -/, and I/sup -/; for Ir(NH/sub 3/)/sub 5/X/sup 2 +/, X = Cl/sup -/ and I/sup -/; and for Ru(NH/sub 3/)/sub 6//sup 2 +/. ..delta..H = 6.1 and 17.4 kcal mol/sup -1/ for the chloride aquation of Rh(NH/sub 3/)/sub 5/Cl/sup 2 +/ and Ir(NH/sub 3/)/sub 5/Cl/sup 2 +/, respectively, and 0.2, 0.2, 2.3, and 7.2 kcal mol/sup -1/ for the ammonia aquation reactions of Rh(NH/sub 3/)/sub 5/Br/sup 2 +/, Rh(NH/sub 3/)/sub 5/I/sup 2 +/, Ir(NH/sub 3/)/sub 5/I/sup 2 +/, and Ru(NH/sub 3/)/sub 6//sup 2 +/, respectively. The reactions were studied in acidic solution so that the product ammonia appeared as ammonium ion. Comparison of the data, including published results for some Cr(III) and Co(III) complexes, allows a tentative ordering of metal-ligand bond strengths in terms of metal ion and in terms of ligand. Thus, D/sub M-NH/sub 3//-D/sub M-OH/sub 2//, D denoting bond dissociation energy, varies with metal M according to the spectrochemical series Ir(III) greater than or equal to Rh(III) approx. Ru(II) > Co(III) > Cr(III).
- Research Organization:
- Univ. of Southern California, Los Angeles
- OSTI ID:
- 6952112
- Journal Information:
- J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 90:25; ISSN JPCHA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201 -- Chemical & Physicochemical Properties
400500* -- Photochemistry
AMMINES
AMMONIA
CALORIMETRY
CHEMICAL REACTIONS
CHEMISTRY
COMPLEXES
DATA
DISSOCIATION HEAT
ENTHALPY
EXPERIMENTAL DATA
HALIDES
HALOGEN COMPOUNDS
HYDRIDES
HYDROGEN COMPOUNDS
INFORMATION
IRIDIUM COMPOUNDS
ISOMERIZATION
LIGANDS
MEDIUM TEMPERATURE
NITROGEN COMPOUNDS
NITROGEN HYDRIDES
NUMERICAL DATA
PHOTOCHEMICAL REACTIONS
PHOTOCHEMISTRY
PHYSICAL PROPERTIES
REACTION HEAT
REFRACTORY METAL COMPOUNDS
RHODIUM COMPOUNDS
RUTHENIUM COMPOUNDS
SOLUTION HEAT
SOLVATION
THERMODYNAMIC PROPERTIES
THERMODYNAMICS
TRANSITION ELEMENT COMPOUNDS
400201 -- Chemical & Physicochemical Properties
400500* -- Photochemistry
AMMINES
AMMONIA
CALORIMETRY
CHEMICAL REACTIONS
CHEMISTRY
COMPLEXES
DATA
DISSOCIATION HEAT
ENTHALPY
EXPERIMENTAL DATA
HALIDES
HALOGEN COMPOUNDS
HYDRIDES
HYDROGEN COMPOUNDS
INFORMATION
IRIDIUM COMPOUNDS
ISOMERIZATION
LIGANDS
MEDIUM TEMPERATURE
NITROGEN COMPOUNDS
NITROGEN HYDRIDES
NUMERICAL DATA
PHOTOCHEMICAL REACTIONS
PHOTOCHEMISTRY
PHYSICAL PROPERTIES
REACTION HEAT
REFRACTORY METAL COMPOUNDS
RHODIUM COMPOUNDS
RUTHENIUM COMPOUNDS
SOLUTION HEAT
SOLVATION
THERMODYNAMIC PROPERTIES
THERMODYNAMICS
TRANSITION ELEMENT COMPOUNDS