Possible reaction mechanisms of hydrogen cyanide formation from oxime blocked isocyanates and related organic compounds during total cyanide analysis

Characterization of palladium species after γ-irradiation of a TBP–alkane–Pd(NO3)2system

“…This species becomes dehydrated and leads to the formation of an α-keto-cyanide ( eqn (2) ), which can be hydrolyzed into carboxylic acid (R–CO–OH) with the departure of HCN ( eqn (3) ). 77 …”

“…Other ways to produce oxime that are consistent with the experimental conditions of the PUREX process were also reported in the literature. 77 In presence of HNO 2 , alcohols can and form nitrous acid ester by esterification ( eqn (4) ). A rearrangement can occur to produce a compound containing both an hydroxyl (–OH) and a nitroso (–N O) groups, i.e.…”

“…Ketones and oximes seem to be a valuable precursor to the formation of HCN among the degradation products formed during g-irradiation. 77,78 In particular, it is interesting to highlight that heating of aldehydes, ketones or alcohols in the presence of hydroxylamine (NH 2 OH) or nitrous acid (HNO 2 ) in acidic media can be responsible for HCN formation. 77 An oxo-oxime can be formed by the addition of HNO 2 or NH 2 -OH to the carbon in a position of the carbonyl group (eqn (1)).…”

“…77,78 In particular, it is interesting to highlight that heating of aldehydes, ketones or alcohols in the presence of hydroxylamine (NH 2 OH) or nitrous acid (HNO 2 ) in acidic media can be responsible for HCN formation. 77 An oxo-oxime can be formed by the addition of HNO 2 or NH 2 -OH to the carbon in a position of the carbonyl group (eqn (1)). This species becomes dehydrated and leads to the formation of an a-keto-cyanide (eqn (2)), which can be hydrolyzed into carboxylic acid (R-CO-OH) with the departure of HCN (eqn (3)).…”

“…77 In presence of HNO 2 , alcohols can and form nitrous acid ester by esterication (eqn (4)). A rearrangement can occur to produce a compound containing both an hydroxyl (-OH) and a nitroso (-N]O) groups, i.e.…”