The reaction of OH with NO2 and the deactivation of O(1D) by CO

✍ Scribed by R. Simonaitis; Julian Heicklen

• Publisher: John Wiley and Sons
• Year: 1972
• Tongue: English
• Weight: 536 KB
• Volume: 4
• Category: Article
• ISSN: 0538-8066
• DOI: 10.1002/kin.550040507

✦ Synopsis

NO, was photolyzed with 2288 A radiation at 300" and 423'K in the presence of H 2 0 , The photolysis produces O(lD) atoms which react with CO, and in some cases excess He. H20 to give H O radicals (3) O(lD) + H20 -+ 2 H 0 or are deactivated by CO to O ( 3 P ) atoms (5) O ~D )

The ratio kJkS is temperature dependent, being 0.33 at 300°K and 0.60 at 423°K. From these two points, the Arrhenius expression is estimated to be k5/k3 = 2.6 exp(-IIOO/RT) where R is in cal/mole -O K .

(1)

or reacts with CO

The O H radical is either removed by NO2

(2)

The ratio kJk" is 0.019 at 300°K and 0.027 at 423"K, and the ratio k2/ko is 1.65X10-5M at 300'K and 2.84X 10-5M at 423'K, with HzO as the chaperone gas, where k" = kl in the high-pressure limit and kO[M] = kl in the low-pressure limit. When combined with the valueofk, = 4.2XlO*exp(-111/RT) M-lsec-l, k" = 6.3X109exp (-340/RT)M-Isec-l and ko = 4.0 X 1012M-2sec-1, independent of temperature for H20 as the chaperone gas.

He is about ' / 8 as efficient as HzO.