Nonmetal Redox Kinetics: Mono-, Di-, and Trichloramine Reactions with Cyanide Ion

Schurter, Lynn M.; Bachelor, Paula P.; Margerum, Dale W.

doi:10.1021/es00004a035

Cited by 38 publications

(34 citation statements)

References 23 publications

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“…Resonances assigned to cyanate, dicyanamide (anion), bicarbonate and carbamoyl phosphate were also observed. Next, a similar experiment was carried out, except with a premade solution of NH 2 Cl prepared from aqueous NH 4 OH and NaOCl. The reaction of NH 2 Cl with cyanide has also been reported to yield ClCN.…”

Section: Resultsmentioning

confidence: 99%

“…Our curiosity was piqued by reports that radiolysis of NaCl solutions generate hypochlorite ( − OCl) through a mechanism thought to be initiated by the scavenging of •OH by Cl − , although mechanisms involving direct ionization of Cl − , as well as H 2 O •+ hole‐scavenging, likely contribute significantly at large chloride concentrations. Moreover, hypochlorous acid (HOCl) as well as chloramine (NH 2 Cl, formed in water from NH 3 and HOCl) react rapidly with − CN to produce ClCN ( k HOCl =1.22•10 9 M –1 s –1 ; [H 3 O + ]‐assisted k NH2Cl =4.32•10 10 M –2 s –1 ). We hypothesized that radiolysis of NaCl solutions containing NH 4 Cl and dilute (∼mM) HCN would yield ClCN, and thereby furnish H 2 NCN by a polar addition‐elimination reaction with NH 3 .…”

Section: Introductionmentioning

confidence: 99%

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Radiolytic Synthesis of Cyanogen Chloride, Cyanamide and Simple Sugar Precursors

Hongo

Yoda

et al. 2018

ChemistrySelect

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Chemical evolution, from simple molecules to complex systems, is fundamental to modern origins of life research, and complex reaction networks are often supposed to have operated on the early Earth. Herein, a variety of compounds useful particularly for RNA synthesis − namely, cyanogen chloride, cyanamide, and nitrile precursors to simple sugars − are produced in short order by a chemical reaction network starting from hydrogen cyanide and driven by gamma radiolysis. The radiolytic yield of cyanamide was found to be proportional to the concentration of chloride, an often overlooked spectator anion. Aqueous irradiation of hydrogen cyanide in the presence of sodium chloride also affords cyanogen chloride, a possible intermediate in the radiolytic synthesis of cyanamide. Meanwhile, the synthesis of simple sugar precursors is proposed to proceed through a Kiliani‐Fischer homologation mechanism made possible by the reducing power of the solvated electron and hydrogen atom. Such a reaction network has the potential to serve as a model for better understanding and engineering chemical evolution of complex mixtures in the laboratory that could have happened on the early Earth.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Radiolytic Synthesis of Cyanogen Chloride, Cyanamide and Simple Sugar Precursors

Hongo

Yoda

et al. 2018

ChemistrySelect

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“…The NH 2 Cl concentration was quantified using the method by Schreiber and Mitch (2005) considering the absorption of NH 2 Cl and dichloramine (NHCl 2 ) at l ¼ 245 and 295 nm (NH 2 Cl: ε 245 nm ¼ 445 M À1 cm À1 , ε 295 nm ¼ 14 M À1 cm À1 ; NHCl 2 : ε 245 nm ¼ 208 M À1 cm À1 , ε 295 nm ¼ 267 M À1 cm À1 ). To check for the presence of trichloramine, the absorbance at 360 nm was analysed (ε 360 nm ¼ 126 M À1 cm À1 ) (Schurter et al, 1995). NH 2 Cl dissociation might be considerable if experiments are conducted at neutral or acidic pH with high NH 2 Cl and phosphate buffer concentrations (Jafvert and Valentine, 1992).…”

Section: Reagentsmentioning

confidence: 99%

Enhanced N-nitrosamine formation in pool water by UV irradiation of chlorinated secondary amines in the presence of monochloramine

et al. 2013

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“…Monochloramine is known to react with iodide, bromide, and cyanide ions 18,24,25 and is most likely to react with thiocyanate as well. The competition with benzoate does not suffer from such side reactions and we believe that the present result is more reliable.…”

Section: Reactions Of Monochloramine With Primary Radicals Of Water Rmentioning

confidence: 99%

Radiolytic Reactions of Monochloramine in Aqueous Solutions

2003

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Monochloramine reacts with hydrated electrons very rapidly, k(NH 2 Cl+e aq -) ) (2.2 ( 0.3) × 10 10 L mol -1 s -1 , to produce • NH 2 radicals. It reacts with • OH radicals more slowly, k(NH 2 Cl+ • OH) ) (5.2 ( 0.6) × 10 8 L mol -1 s -1 , to produce • NHCl radicals. While • NH 2 exhibits an absorption peak at 530 nm, with a molar absorption coefficient 530 ) 80 L mol -1 cm -1 , • NHCl exhibits two peaks at 330 and 580 nm, 330 ) (85 ( 30) L mol -1 cm -1 and 580 ) (56 ( 30) L mol -1 cm -1 . The • NHCl radical undergoes self-decay and can react also with O 2 to form a peroxyl radical. It is suggested that the peroxyl radical exists in equilibrium NHClO 2 • / • NHCl + O 2 with an estimated equilibrium constant of (3 ( 2) × 10 -3 mol L -1 . The reaction of chloramine with the carbonate radical is suggested to form a complex [CO 3 NH 2 Cl] •-with k f ) 2.5 × 10 5 L mol -1 s -1 and k r ) 4 × 10 2 s -1 , and this complex decomposes with k ) 7 × 10 2 s -1 to form • NHCl.

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Nonmetal Redox Kinetics: Mono-, Di-, and Trichloramine Reactions with Cyanide Ion

Cited by 38 publications

References 23 publications

Radiolytic Synthesis of Cyanogen Chloride, Cyanamide and Simple Sugar Precursors

Radiolytic Synthesis of Cyanogen Chloride, Cyanamide and Simple Sugar Precursors

Enhanced N-nitrosamine formation in pool water by UV irradiation of chlorinated secondary amines in the presence of monochloramine

Radiolytic Reactions of Monochloramine in Aqueous Solutions

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