TY - JOUR
T1 - An electron spin resonance investigation of the reactions in irradiated aqueous solutions of hydrogen cyanide and the cyanide ion
AU - Behar, D.
AU - Fessenden, Richard W.
PY - 1972
Y1 - 1972
N2 - 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-.
AB - 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-.
UR - http://www.scopus.com/inward/record.url?scp=0010786307&partnerID=8YFLogxK
U2 - 10.1021/j100670a009
DO - 10.1021/j100670a009
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AN - SCOPUS:0010786307
SN - 0022-3654
VL - 76
SP - 3945
EP - 3950
JO - Journal of Physical Chemistry
JF - Journal of Physical Chemistry
IS - 26
ER -