The Transfer of Oxygen Atoms in Oxidation—Reduction Reactions. III. The Reaction of Halogenates with Sulfite in Aqueous Solution

Halperin, J.; Taube, Henry

doi:10.1021/ja01122a026

Cited by 66 publications

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“…In addition to these reactions with organic compounds, which might involve oxygen atom transfer, peroxymonosulfate can be reduced by metal ions, ppssibly producing the highly reactive free radicals, S04 or OH, as it does upon reaction with e,q- (92), e.g. Other reactions of bisulfite are known to involve oxygen atom transfer (93)(94)(95)(96)(97).…”

Section: Reactions Of Peroxysulfate Radicalmentioning

confidence: 99%

Free-radical chemistry of sulfite.

Neta¹,

Huie²

1985

Environ Health Perspect

273

154

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Section: Reactions Of Peroxysulfate Radicalmentioning

confidence: 99%

Free-radical chemistry of sulfite.

Neta¹,

Huie²

1985

Environ Health Perspect

273

154

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“…The function of H+ presumably is to strip off 0-in an SNI mechanism, or to withdraw electrons from the center undergoing nucleophilic attack in an SN2 mechanism. The labilization by H+ of anions for exchange, at least in a qualitative way, has been noted in numerous other cases: among them CIO,- (14), POi" (44), Cr04- (86). The claim made in the earlier literature (42,49) that substitution by OH-in the anion provides a path for exchange in no case has been sub stantiated by later, more thorough work.…”

Section: Rates and Mechanism Of Oxygen Exchange Between Dissolved Submentioning

confidence: 97%

“…Inorganic molecules and anions.-The following inorganic substances have been found to exchange oxygen slowly enough in neutral or alkaline aqueous solution so that hold-back under these conditions is easily observed (oxy anions become more labile to exchange in acid solution-see section on Rates and Mechanisms of Exchange dealing with inorganic anions) : CIO,-(34, 35), CI03- (34,35,36), CIO, (14), C102- (14), CIo-(37), Br03- (35), Bro-(37), 0, (38), 03 (39), H20, (40,41), SO,= (34,35,38,42,43,44), S03= (35,45), S203= (45), SeOr (35), NOa- (34,35,36), N02- (35), N,Oa= (47), N20 (48), N202= (47), phosphates (34,42,44,46,49), H2P03-, H2P02-(SO), C03= (35,46,51), Et3 SiOH (52), �8SiOH (52), CrO,- (34,35,45), MnO.- (35,45). For these substances it is demonstrated that oxygen atoms as shown in the formulas are held distinct from solvent oxygen, and thus for any of them forms in which contained oxygen becomes equivalent to solvent oxygen are ruled out as being readily accessible (e.g., for CI(I): CI(OHh-or CI++20H-) .…”

Section: Oxygen Hold-back By Dissolved Substancesmentioning

confidence: 98%

“…is derived from O2• Oxidations by oxy-halogen compounds. Fairly extensive tracer studies have been made with halogen-oxygen species as oxidizing agents (14). With S03 as reducing agent and ClOa-, CIOz, ClO:-, or Br08-as oxidizing agents, the oxygen of the oxidizing agent, except for a defect of ca.…”

Section: Oxidation-reduction Reactionsmentioning

confidence: 99%

“…Sulfates (14) have been handled by reducing BaSO, with C using induc tion heating to avoid the exchange with glass parts of the system, phosphates by reduction with C (15) or by removing H20 from KH2PO, (16) by heating the salt. Anbar & Taube (17) have shown that oxygen is released from Ag2SO, and Ag3P04 when they are strongly heated (Pt crucible in an induction fur nace) .…”

Section: Techniquesmentioning

confidence: 99%

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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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Chlorine Oxygen Acids and Salts, Dichlorine Monoxide, Hypochlorous Acid, and Hypochlorites

Wojtowicz

2000

Kirk-Othmer Encyclopedia of Chemical Technology

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The hydrolysis of chlorine gives rise to a pH‐dependent complex system involving no less than six equilibria in which the oxidizing power of the parent element is preserved in hypochlorous acid, chlorine monoxide, and hypochlorite. The physical and chemical aspects of this unique family of compounds, including organic and other nonmetal hypochlorites, are outlined, their preparation and manufacturing processes are surveyed, and important uses are cited. Corrosion problems and potential hazards in handling and use of these compounds are also discussed. Hypochlorous acid is the active biocidal agent when hypochlorites are employed in disinfection and sanitation. It is an intermediate in the manufacture of hypochlorites, chloramines, and chlorohydrins. A process for production of HOCl in concentrations as high as 60% has recently been developed. The commercially important hypochlorites are Ca(OCl) 2 , NaOCl solution, LiOCl, chlorinated trisodium phosphate, and to a lesser extent hemibasic Ca(OCl) 2 and bleaching powder. They are used primarily in sanitation and bleaching applications. Although the use of chloroisocyanurates in swimming pool sanitation is increasing, hypochlorites remain the dominant products in this area. The most important solid hypochlorite is Ca(OCl) 2 , which is marketed in partially hydrated form and to a lesser extent as an almost anhydrous product. Several new processes for its manufacture are described. Continued research interest involve use of hypochlorites for selective epoxidation, oxidation, and chlorination, and use of chlorine monoxide as a highly selective agent for aromatic ring and side chain chlorination.

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The Transfer of Oxygen Atoms in Oxidation—Reduction Reactions. III. The Reaction of Halogenates with Sulfite in Aqueous Solution

Cited by 66 publications

References 0 publications

Free-radical chemistry of sulfite.

Free-radical chemistry of sulfite.

Applications of Oxygen Isotopes in Chemical Studies

Chlorine Oxygen Acids and Salts, Dichlorine Monoxide, Hypochlorous Acid, and Hypochlorites

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