Kinetics of oxygen exchange between bisulfite ion and water as studied by oxygen-17 nuclear magnetic resonance spectroscopy

Technical Report · Wed Aug 01 04:00:00 EDT 1984

DOI:https://doi.org/10.2172/6507790· OSTI ID:6507790

Horner, D A

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 Lab., CA (USA)
• DOE Contract Number: AC03-76SF00098
• OSTI ID: 6507790
• Report Number(s): LBL-18297; ON: DE85001866
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400203* -- Isotope Exchange & Isotope Separation-- (-1987)
AQUEOUS SOLUTIONS
DISPERSIONS
EVEN-ODD NUCLEI
HYDROGEN COMPOUNDS
ISOMERS
ISOTOPES
ISOTOPIC EXCHANGE
LIGHT NUCLEI
MAGNETIC RESONANCE
MIXTURES
NUCLEAR MAGNETIC RESONANCE
NUCLEI
OXYGEN 17
OXYGEN COMPOUNDS
OXYGEN ISOTOPES
PH VALUE
RELAXATION
RESONANCE
SOLUTIONS
SPECTRA
STABLE ISOTOPES
SULFITES
SULFUR COMPOUNDS
WATER