Study of the complexation kinetics of Cs/sup +/ ion with dibenzo-30-crown-10 in some nonaqueous solvents by /sup 133/Cs NMR

Journal Article · Thu Jan 14 04:00:00 EST 1988 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100312a032· OSTI ID:5486039

Shamsipur, M; Popov, A I

The exchange kinetics of the complexation of the cesium ion with dibenzo-30-crown-10 were studied in nitromethane, acetonitrile, propylene carbonate, and methanol solutions by cesium-133 NMR line-shape analysis. In the last three solvents, when the temperature is below -10/sup 0/C, the predominant mechanism for the exchange of the Cs/sup +/ ion between the solvated and complexed sites is the bimolecular process. In nitromethane solutions, at all temperatures studied, and in propylene carbonate and methanol solutions at -10/sup 0/C, the exchange process proceeds by the dissociation pathway. The activation parameters E/sub a/, ..delta..H*, ..delta..S*, and ..delta..G double dagger for the exchange have been determined. In systems where the exchange mechanism is bimolecular, the free energy barrier for the exchange process appears to be independent of the solvent.

• Research Organization: Michigan State Univ., East Lansing
• OSTI ID: 5486039
• Journal Information: J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 92:1; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400202* -- Isotope Effects
Isotope Exchange
& Isotope Separation
ACETONITRILE
ACTIVATION ENERGY
ALCOHOLS
ALKALI METAL COMPOUNDS
ALKALI METAL ISOTOPES
CATIONS
CESIUM 133
CESIUM COMPOUNDS
CESIUM ISOTOPES
CHARGED PARTICLES
CHEMICAL EXPLOSIVES
CHEMICAL REACTION KINETICS
COMPLEXES
COMPLEXOMETRY
DATA
ENERGY
EXPERIMENTAL DATA
EXPLOSIVES
FREE ENTHALPY
GLYCOLS
HYDROXY COMPOUNDS
INFORMATION
IONS
ISOTOPES
KINETICS
LIFETIME
MAGNETIC RESONANCE
METHANOL
NITRILES
NITRO COMPOUNDS
NITROMETHANE
NMR SPECTRA
NUCLEAR MAGNETIC RESONANCE
NUCLEI
NUMERICAL DATA
ODD-EVEN NUCLEI
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC POLYMERS
PHYSICAL PROPERTIES
POLYETHYLENE GLYCOLS
POLYMERS
REACTION KINETICS
RESONANCE
SPECTRA
STABLE ISOTOPES
TEMPERATURE DEPENDENCE
THERMODYNAMIC PROPERTIES