Oxygen Atom Transfer in Oxidation—Reduction Reactions. II. The Mechanism of the Sulfite—Nitrite Reaction

Rutenberg, A. C.; Halperin, J.; Taube, Henry

doi:10.1021/ja01153a536

Cited by 12 publications

(7 citation statements)

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“…at room temperature there was no exchange of the oxygen atoms of sulfite with the oxygen of water, and that all the oxygen used in the oxidation of sulfite to sulfate came from the oxidizing agent and none from the water. Rutenberg, Halperin, and Taube (96) found that in the hydrolysis of the compounds (KSOs^NOH and (KSOsisN -2H20, formed as intermediates during the oxidation of sulfite by nitrite, no exchange of oxygen between sulfite bound in the complexes and the solvent occurred. This observation strengthens the postulate that the complexes are formed by internal nitrogen-sulfur bonds.…”

Section: Chemical Applications Of the Isotopes Of Oxygenmentioning

confidence: 99%

The Chemistry of the Isotopes of Oxygen.

Dole¹

1952

Chem. Rev.

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Section: Chemical Applications Of the Isotopes Of Oxygenmentioning

confidence: 99%

The Chemistry of the Isotopes of Oxygen.

Dole¹

1952

Chem. Rev.

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“…It is surprising that the technique would still be useful with such a large excess of SO32"". At this point, the reason isn't very clear except that one would expect the reaction of SO32-with N02~i n acid solution to be as follows (10): 2H+ + N02" + 2S032" + H20 = NH3OH+ + 2S042-Furthermore, the reaction product, NH2OH, as shown in Table I, is a positive interferent and experiments have shown that NH2OH will react with the dye and cause fluorescence enhancement under identical acid and base conditions as the N02~.…”

Section: Resultsmentioning

confidence: 99%

Measurement of sub-ppb by volume levels of atmospheric nitrogen dioxide using an alkaline trapping solution and spectrofluorometric analysis

Axelrod¹,

Pickett²,

Engel³

1975

Anal. Chem.

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“…The reactions of <l>H with H2S04, which produces <l>S03H as an intermediate stage, and which on reaction in alkali forms <l>ONa having oxygen derived from the solvent (118), is an example in the last category. Another is the reaction of nitrite and sulfite forming as final products NH20H and 504=, The intermediate HON(S03h-can be isolated in this system, and when this is hydrolyzed solvent oxygen is placed on the S04- (140). These examples taken in the context of the first few in which the oxygen atom is shown to be transferred, will serve to show that the path of oxygen for reactions involving oxy-ions requires experimental investigation.…”

Section: Oxidation-reduction Reactionsmentioning

confidence: 94%

Applications of Oxygen Isotopes in Chemical Studies

Taube¹

1956

Annu. Rev. Nucl. Sci.

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The choice of the general subject of this article requires no apology, but the choice of the specific material to fit to the space allotted does. The limita tions and research interests of the reviewer were a governing factor in mak ing the selection, but also the consideration entered that the effects of the major omissions are tempered by other recent reviews in which much of the material omitted is discussed. Thus the important work in geochemistry involving oxygen isotopes is discussed in excellent reviews by Dole (I), and more recently by Craig & Boata (2). The work on heterogenous systems is discussed more completely in the article by Dole. It is hoped in this connec tion that a general article on the application of isotopes in the study of heterogeneous catalysis, induding work with oxygen isotopes, will be forth coming. In the subjects chosen for review, an effort has been made to be com plete ; and earlier literature as well as the more recent has been referred to. When work which is within the scope of the subject matter is not cited, it is because of oversight or because the work is dealt with in a more general article by the same author.The present article stresses the application of oxygen isotopes to the study of chemical phenomena in homogeneous solution. Much of the work exploiting oxygen isotope effects has been done for such systems. For reac tions of oxygen-containing substances in an oxide-labile solvent such as water, isotope studies can answer important questions which no other method can answer as directly; and they have been of great help in defining the nature of the solvent and of the substances dissolved in it, and in exposing the mechanisms of reactions in solution. TECHNIQUESIn the work reviewed, mainly the oxygen isotopes of mass 18 and 16 come into question. The mass spectrometric method of measuring isotope ratios has almost completely supplanted that depending on the determination of density differences in water. With care, commercial instruments can measure differences to a precision of 1 part in 1000 in O2 or CO2 of normal oxygen isotopic composition. With specially designed instruments (3), a precision of one part in approximately 10,000 on CO2 can be attained.When the oxygen is available as water, an accurate method (4) of isotopic assay is equilibration of CO2 with the H20, followed by measurement of the isotopic ratio in the CO2• Dostrovsky & Klein (5) have described the high temperature equilibration of CO2 and H20, and have derived an equation 1 The survey of literature pertaining to this review was completed in January, 1956.

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Oxygen Atom Transfer in Oxidation—Reduction Reactions. II. The Mechanism of the Sulfite—Nitrite Reaction

Cited by 12 publications

References 0 publications

The Chemistry of the Isotopes of Oxygen.

The Chemistry of the Isotopes of Oxygen.

Measurement of sub-ppb by volume levels of atmospheric nitrogen dioxide using an alkaline trapping solution and spectrofluorometric analysis

Applications of Oxygen Isotopes in Chemical Studies

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