Kinetics of oxygen exchange between bisulfite ion and water as studied by oxygen-17 nuclear magnetic resonance spectroscopy
The nuclear magnetic relaxation times of oxygen-17 have been measured in aqueous sodium bisulfite solutions in the pH range from 2.5 to 5 as a function of temperature, pH, and S(IV) concentration, at an ionic strength of 1.0 m. The rate law for oxygen exchange between bisulfite ion and water was obtained from an analysis of the data, and is consistent with oxygen exchange occurring via the reaction SO/sub 2/ + H/sub 2/O right reversible H/sup +/ + SHO/sub 3//sup -/. The value of k/sub -1/ is in agreement with relaxation measurements. Direct spectroscopic evidence was found for the existence of two isomers of bisulfite ion: one with the proton bonded to the sulfur (HSO/sub 3//sup -/) and the other with the proton bonded to an oxygen (SO/sub 3/H/sup -/). (The symbol SHO/sub 3//sup -/ in the above chemical equation refers to both isomeric forms of bisulfite ion.) The relative amounts of the two isomers were determined as a function of temperature, and the rate and mechanism of oxygen exchange between the two was investigated. One of the two isomers, presumably SO/sub 3/H/sup -/, exchanges oxygens with water much more rapidly than does the other. A two-pulse sequence was developed which greatly diminished the solvent peak in the NMR spectrum.
- Research Organization:
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- DOE Contract Number:
- AC03-76SF00098
- OSTI ID:
- 6507790
- Report Number(s):
- LBL-18297; ON: DE85001866
- Resource Relation:
- Other Information: Thesis
- Country of Publication:
- United States
- Language:
- English
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Kinetics of oxygen exchange between bisulfite ion and water as studied by oxygen-17 nuclear magnetic resonance spectroscopy
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
OXYGEN 17
ISOTOPIC EXCHANGE
AQUEOUS SOLUTIONS
ISOMERS
NUCLEAR MAGNETIC RESONANCE
PH VALUE
RELAXATION
SPECTRA
SULFITES
WATER
DISPERSIONS
EVEN-ODD NUCLEI
HYDROGEN COMPOUNDS
ISOTOPES
LIGHT NUCLEI
MAGNETIC RESONANCE
MIXTURES
NUCLEI
OXYGEN COMPOUNDS
OXYGEN ISOTOPES
RESONANCE
SOLUTIONS
STABLE ISOTOPES
SULFUR COMPOUNDS
400203* - Isotope Exchange & Isotope Separation- (-1987)