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Professor David L. Allara, Department of Chemistry,
185 MRI Building, 230 Innovation Boulevard, Penn State Univ., University Park PA 16802 Distinguished professor Sidney W. Benson Scientific Co-Director Emertitus, Loker Hydrocarbon Research Institute, University Park - MC1661 University of Southern California Los Angeles CA 90089-1661 Dr Michael Cowperthwaite 1536 Bittern Avenue Sunnyvale CA 94087 |
Professor Dan McElroy, Computer Information Systems
San Jose City College, 2100 Moorpark Avenue San Jose CA 95128-2799 Bob Shaw 191 East El Camino Real Spc 245 Mountain View CA 94040-2708 (accountable for any errors) Frederick Armstrong Shaul zap technologies (article web hosting) |
2H2 + 2NO -> 2H2O + N2 [0]
have been re-interpreted using thermochemical kinetics.
H2 <-> 2H [H2 equilibrium] HNO <-> H + NO [HNO equilibrium] HON <-> H + NO [HON equilibrium] 2HNO -> H2O + N2O [1] 2HON -> H2O + N2O [2] HNO + NO -> HO + N2O [3] HON + NO -> HO + N2O [4] HO + H2 -> H2O + H [5] H + N2O -> HO + N2 [6]
Reactions [1] through [4] are rate determining.
-d[N2]/dt = a[H2] + b[H2]0.5 [7]
a = {(k1/KHNO)2) + (k2/KHON)2)}KH2[NO]2 [8]
b = {(k3/KHNO) + (k4/KHON)}(KH2)0.5[NO]2 [9]
a = 10-3.1s-1 b = 10-3.9M0.5s-1
x/M form of log(x/M) log(x/M) at 1074 K
KH2 3.3 - (103.7)/theta) -17.9
KHNO 3.6 - (48.1)/theta) -6.2
KHON 3.6 - (23.2)/theta) -1.1
where theta is 10-32.303RT kcal/mole, 4.91 kcal/mole at 1074 K.
At 1074 K, 300 mm NO = 10-2.34 M, & 1 mm/(100s) = 10-6.82 M s-1.
If reaction [2] is ignored, then k1 = 107.1M-1s-1, in line with results determined by other workers.
From literature, k3 = 104.2 M-1 s-1 at 1074 K.
This gives k4 = 108.9 M-1 s-1, compared with 109.5 M-1 s-1, estimated at a meeting of the Western States Section of the Combustion Institute at Stanford in 1995.
Because the rate of [1] is almost independent of temperature, if the hydrogen equilibrium is set up, say catalytically, the overallreaction will go at a measurable rate at much lower temperatures.
We thank all those who have helped.