TY - JOUR
T1 - An electron spin resonance study of the radiolysis of aqueous solutions of cyanate ion
AU - Behar, D.
AU - Fessenden, Richard W.
PY - 1974
Y1 - 1974
N2 - The in situ radiolysis-esr method has been used to investigate the radicals produced in aqueous solutions of cyanate ion (NCO-) by high-energy electron irradiation. Over the pH range 3.6-12.4, N2O-saturated solutions give rise to a proton-containing radical with the esr parameters aN = 13.73, aH = 10.87 G, and g = 2.00425. From the dependence of the intensity of this spectrum upon flow rate and the concentration of NCO- it is concluded that the radical is a primary product and most probably has the structure HNCO2-. Over the pH range 6.5-10.5 another radical which contains two nitrogen atoms and has the parameters aN = 9.82, aN′ = 5.90, aH = 7.84, and g = 2.00404 is observed. This radical can best be assigned as -O2CNHNCO2- formed by a secondary reaction of OH with the dimer of the primary radical. Above about pH 12 yet another radical is found which also seems to be a secondary product. On the basis of earlier studies this radical can be assigned the structure -O2CNO2-. No radicals resulting from the reaction of eaq- with cyanate were found. Radicals which may have the structure RO2CN- were produced by allowing methyl and ethyl carbamate to react with HOCl and allowing the resultant N-chloro compounds to react with eaq- in basic solution. The spectra for the two esters were similar in their gross features with aN ∼ 11 G and g ∼ 2.0048.
AB - The in situ radiolysis-esr method has been used to investigate the radicals produced in aqueous solutions of cyanate ion (NCO-) by high-energy electron irradiation. Over the pH range 3.6-12.4, N2O-saturated solutions give rise to a proton-containing radical with the esr parameters aN = 13.73, aH = 10.87 G, and g = 2.00425. From the dependence of the intensity of this spectrum upon flow rate and the concentration of NCO- it is concluded that the radical is a primary product and most probably has the structure HNCO2-. Over the pH range 6.5-10.5 another radical which contains two nitrogen atoms and has the parameters aN = 9.82, aN′ = 5.90, aH = 7.84, and g = 2.00404 is observed. This radical can best be assigned as -O2CNHNCO2- formed by a secondary reaction of OH with the dimer of the primary radical. Above about pH 12 yet another radical is found which also seems to be a secondary product. On the basis of earlier studies this radical can be assigned the structure -O2CNO2-. No radicals resulting from the reaction of eaq- with cyanate were found. Radicals which may have the structure RO2CN- were produced by allowing methyl and ethyl carbamate to react with HOCl and allowing the resultant N-chloro compounds to react with eaq- in basic solution. The spectra for the two esters were similar in their gross features with aN ∼ 11 G and g ∼ 2.0048.
UR - http://www.scopus.com/inward/record.url?scp=0011195578&partnerID=8YFLogxK
U2 - 10.1021/j100604a005
DO - 10.1021/j100604a005
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AN - SCOPUS:0011195578
SN - 0022-3654
VL - 78
SP - 1074
EP - 1078
JO - Journal of Physical Chemistry
JF - Journal of Physical Chemistry
IS - 11
ER -