The following is a simplified mechanism for predicting O3 formation in
photochemical smog systems:
HC+OH ? a RO2+P , k1 Hydrocarbon loss and product formation
P+OH ? b RO2+Loss, k2 Product Loss
P+hv ? c RO2+Loss. kp Product Photolysis
RO2+NO ?NO2+Loss, k3 NO Photooxidation
NO2+hv?NO+O3, k4 forward Photostationary State
k5 backward
Everything?Loss, kd Dilution
In this mechanism HO2 radicals are lumped up with RO2, and, to a first
approximation, all RO2 are assumed to react with NO. This mechanism
does not predict the OH concentration, taking instead the quantity
k1[OH]=M as an input hydrocarbon reactivity parameter.
Show that the mechanism can be used to predict the number of net NO
photo oxidations produced per hydrocarbons consumed,
d([NO]-[O3]) / d[HC] = (m(a[HC]+b (k2/k1) [P])+c kp[P]+kd([NO]-[O3])) / (ma+kd)[HC]
Use of the quantity [NO]-[O3] as net NO oxidized effectively cancels
out the photostationary state; thus ozone is simply ?negative nitric
oxide? |