The reduction of MONO by HNO and NH3 has been investigated by means, of ab
initio molecular orbital and transition-state theory (TST) calculations. Th
e main reaction channels for the HNO + trans-MONO (cis-HONO) reactions are
those proceeding via five-member ring transition states, leading to the pro
duction of NO and H2O. In the temperature range 300-1000 K, TST calculation
s predict an A factor of 2.25 x 10(10) cm(3) mol(-1) s(-1) (or 3.63 x 10(10
) cm(3) mol(-1) s(-1)) and an apparent activation energy of 20.9 kcal/mol (
or 21.9 kcal/mol) for the HNO + trans-HONO (or cis-HONO) reaction. In the N
H3 + HONO system, the reaction NH3 + cis/trans-HONO --> H2NNO + H2O with ba
rrier heights centering around 34 kcal/mol can occur at high temperatures.
The reversible H-atom exchange reaction NH3 + cis-HONO double left right ar
row H2NH-O(H)NO double left right arrow NH2H + cis-HONO occurs readily. The
calculated rate constant for the reaction at 300 K is 1.06 x 10(6) cm(3) m
ol(-1) s(-1), in reasonable agreement with the experimental value of 2.2 x
10(6) cm(3) mol(-1) s(-1).