Abstract
The kinetics of the reversible reactions HONO+NH 3⇌H 3N-HONO (1) was studied by monitoring trans-HONO relaxation kinetics. The rate of approach towards equilibrium was studied as a function of the ammonia concentration to obtain values of the rate constants for the forward and reverse reactions as well as the equilibrium constant. At 298 K we have determined the following values for the forward rate constant and the equilibrium constant, k 1f=(2.2±0.2)×10 3 M −1 s −1 and K C=(1.5±0.2)×10 5 M −1. The equilibium constant was determined at temperatures in the range of 287–319 K, and from the observed temperature dependence expressed in terms of the van 't Hoff equation we have derived the following values of Δ H 298 0=−11.8±0.8 kcal/mol and Δ S 298 0=−26.7±1.0 cal/mol K. Theoretical investigations of the structure and thermochemistry of the H 3N-HONO hydrogen bonded complex were carried out on the electron correlation level and 6-311+G(2df, 2pd) basis set. The calculated binding energy is −10.1 kcal/mol while Δ H 298 0=−8.1 kcal/mol and Δ S 298 0=−26.70 cal/mol K.
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