An electron spin resonance investigation of the reactions in irradiated aqueous solutions of hydrogen cyanide and the cyanide ion

D. Behar, Richard W. Fessenden*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

31 Scopus citations

Abstract

Use of the in situ radiolysis-esr method has shown that the reactions of H and OH with HCN in acid solutions yield the radicals H2C=N (aH = 87.2, aN = 10.2 G, g = 2.0028) and HC(OH)=N (aH = 54.40, aOHH = 0.89, aN = 10.14 G, g = 2.00322), respectively. The pK for the dissociation of the OH proton in the latter radical is estimated to be ∼5. Scavenging of eaq- with HCN also yields H2C=N. The reaction of OH and O- with CN- in alkaline solutions was found to produce the radical ·CONH2 as observed either directly at pH ∼10 or by radical trapping with CH2=NO2- at higher pH. Exactly parallel behavior was found for CN- and HCONH2 in basic solutions. However, HCONH2 yielded only ·CONH2 in acid and neutral solutions and no rearrangement of this radical to HC(OH)=N was found. The adduct to CH2==NO2- found in CN- solutions and previously identified as NCCH2NO2- must now be assigned the structure H2NCOCH2NO2-.

Original languageEnglish
Pages (from-to)3945-3950
Number of pages6
JournalJournal of Physical Chemistry
Volume76
Issue number26
DOIs
StatePublished - 1972
Externally publishedYes

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