The production of significant concentrations of O(3P) in the gas phase reaction of hydrogen atoms with ozone in a fast flow discharge system at 1.1±0.1 Torr total pressure in Ar and at room temperature has been reported earlier. These yields were observed to be independent of the concentration of known deactivators of OH (v = 9) such as O2 and CO2. We report here the results of detailed studies of the yields of O(3P) and ground state OH(X2πi)v = 0 (OH) using resonance fluorescence under a wide variety of reaction conditions. It is shown that the highest yields of O(3P), 27±2% of the calculated loss of O3 are observed when H is present in excess and the flow tube is coated with a halocarbon wax. The yields are substantially lower when O3 is present in excess and increases as [O3]0 increases. In addition, in an excess of either reagent, the O(3P) yields are lower when the walls of the flow tube are coated with boric acid, which is known to deactivate the vibrationally excited OH produced in the initial reaction of H with O3. Addition of NO decreased the yield of O(3P), and increased the yield of OH. These results suggest that secondary reactions of OH, likely with H and O3, are responsible for the production of O(3P), and that a second primary reaction channel, H+O3→HO2+O(3P) [Eq. (lb)] accounts for ?2% of the net reaction.

1.
See, for example,
J. C.
Polanyi
and
J. J.
Sloan
,
Int. J. Chem. Kinet. Symp.
1
,
51
(
1975
), and references therein.
2.
K. G.
Anlauf
,
R. G.
McDonald
, and
J. C.
Polanyi
,
Chem. Phys. Lett.
1
,
619
(
1968
).
3.
P. E.
Charters
,
R. G.
McDonald
, and
J. C.
Polanyi
,
Appl. Opt.
10
,
1747
(
1971
).
4.
F.
Kaufman
and
R. D.
Levine
,
Chem. Phys. Lett.
54
,
407
(
1978
).
5.
J. Heicklen, Atmospheric Chemistry (Academic, New York, 1976), Chap. 2, and references therein.
6.
“Chlorofluoromethanes and the Stratosphere,” edited by R. D. Hudson,
NASA Ref. Publ.
1010
(
1977
). and references therein.
7.
A. F.
Nagy
,
S. C.
Liu
, and
D. J.
Baker
,
Geophys. Res. Lett.
3
,
731
(
1976
).
8.
G. E.
Streit
,
G. Z.
Whitten
, and
H. S.
Johnston
,
Geophys. Res. Lett.
3
,
521
(
1976
).
9.
E. J.
Llewellyn
and
B. H.
Long
,
Can. J. Phys.
56
,
581
(
1978
);
E. J.
Lelewellyn
,
B. H.
Long
, and
B. H.
Solheim
,
Planet. Space Sci.
26
,
525
(
1978
) and references therein.
10.
H.
Takahashi
and
P. P.
Batista
,
Planet. Space Sci.
28
,
559
(
1980
).
11.
See, for example, R. Atkinson, K. R. Darnall, A. C. Lloyd, A. M. Winer, and J. N. Pitts, Jr., in Advances in Photochemistry, edited by J. N. Pitts, Jr., G. S. Hammond, and K. Gollnick (Wiley, New York, 1979), Vol. 11, pp. 375–488;
D. D. Drysdale and A. C. Lloyd, in Oxidation Combustion Reviews, edited by C. F. H. Tipper (Elsevier, Amsterdam, 1970), Vol. 4, pp. 157–250;
W. E.
Wilson
, Jr.
,
J. Phys. Chem. Ref. Data
1
,
535
(
1972
), and references therein.
12.
B. J.
Finlayson
,
J. N.
Pitts
,Jr.
, and
R.
Atkinson
,
J. Am. Chem. Soc.
96
,
5356
(
1974
), and references therein;
J. T.
Herron
and
R. E.
Huie
,
J. Am. Chem. Soc.
99
,
5430
(
1977
);
H. Niki, in “Chemical Kinetic Data Needs for Modeling the Lower Troposphere,” edited by J. T. Herron, R. E. Huie, and J. A. Hodgeson, Natl. Bur. Stand. Publ. 557 (1979);
M. C.
Dodge
and
R. R.
Arnts
,
Int. J. Chem. Kinet.
11
,
399
(
1979
).
13.
B. B.
Krieger
and
R. H.
Kummler
,
J. Phys. Chem.
81
,
2493
(
1977
), and references therein.
14.
A. B.
Meinel
,
Astrophys. J.
111
,
207
,
433
(
1950
).
15.
D. R.
Bates
and
M.
Nicolet
,
J. Geophys. Res.
55
,
301
(
1950
).
16.
J. D.
McKinley
,
D.
Garvin
, and
M. J.
Boudart
,
J. Chem. Phys.
23
,
784
(
1955
).
17.
T. M.
Cawthon
, Jr.
and
J. D.
McKinley
, Jr.
,
J. Chem. Phys.
25
,
585
(
1956
).
18.
F.
Kraus
,
Z. Naturforsch. Teil A
12
,
479
(
1957
).
19.
D.
Garvin
,
J. Am. Chem. Soc.
81
,
3173
(
1959
).
20.
D.
Garvin
,
H. P.
Broida
, and
H. J.
Kostkowski
,
J. Chem. Phys.
32
,
880
(
1960
).
21.
G. E.
Streit
and
H. S.
Johnston
,
J. Chem. Phys.
64
,
95
(
1976
), and references therein.
22.
L. F.
Phillips
and
H. I.
Schiff
,
J. Chem. Phys.
37
,
1233
(
1962
);
M. A. A.
Clyne
and
P. B.
Monkhouse
,
J. Chem. Soc. Faraday Trans. 2
73
,
298
(
1977
);
J. H.
Lee
,
J. V.
Michael
,
W. A.
Payne
, and
L. J.
Stief
,
J. Chem. Phys.
69
,
350
(
1978
);
L. F.
Keyser
,
J. Phys. Chem.
83
,
645
(
1979
).
23.
B. J. Finlayson‐Pitts and T. E. Kleindienst (unpublished data).
24.
B. J.
Finlayson‐Pitts
and
T. E.
Kleindienst
,
J. Chem. Phys.
70
,
4804
(
1979
).
25.
B. J. Finlayson‐Pitts and T. E. Kleindienst, J. Chem. Phys. (in press).
26.
Throughout this paper vibrationally excited OH is designated as OH†. Where a specific vibrational level is discussed, it is written as OH‡ (ν). Ground state OH, i.e., ν = 0, is written as OH.
27.
M. J.
Kurylo
and
A. H.
Laufer
,
J. Chem. Phys.
70
,
2032
(
1979
).
28.
C. J.
Howard
and
B. J.
Finlayson‐Pitts
,
J. Chem. Phys.
72
,
3842
(
1980
).
29.
N.
Washida
,
H.
Akimoto
, and
M.
Okuda
,
J. Chem. Phys.
72
,
5781
(
1980
).
30.
A. E.
Potter
,Jr.
,
R. N.
Coltharp
, and
S. D.
Worley
,
J. Chem. Phys.
54
,
992
(
1971
);
R. N.
Coltharp
,
S. D.
Worley
, and
A. E.
Potter
,
Appl. Opt.
10
,
1786
(
1971
);
S. D.
Worley
,
R. N.
Coltharp
, and
A. E.
Potter
,
J. Chem. Phys.
55
,
2608
(
1971
);
S. D.
Worley
,
R. N.
Coltharp
, and
A. E.
Potter
, Jr.
,
J. Phys. Chem.
76
,
1151
(
1972
), and references therein.
31.
J. E.
Spencer
and
G. P.
Glass
,
Chem. Phys.
15
,
35
(
1976
).
32.
J. E. Spencer, H. Endo, and G. P. Glass, 16th Symposium (International) on Combustion (The Combustion Institute, Pittsburgh, 1977), pp. 339–348;
J. E.
Spencer
and
G. P.
Glass
,
Int. J. Chem. Kinet.
11
,
97
,
111
(
1977
).
33.
D. H.
Jaffer
and
I. W. M.
Smith
,
Faraday Discuss. Chem. Soc.
67
,
212
(
1979
).
34.
T. E.
Kleindienst
and
B. J.
Finlayson‐Pitts
,
Chem. Phys. Lett.
61
,
300
(
1979
), and references therein.
35.
R. F. Hampson, “Chemical Kinetic and Photochemical Data Sheets for Atmospheric Reactions,” Report No. FAA‐EE‐80‐17, U.S. Department of Transportation, Federal Aviation Administration, Office of Environment and Energy, High Altitude Pollution Program, Washington, D.C. 20591, April 1980, and references therein.
36.
^Concentrations and second order rate constants are given throughout in units of molecules, atoms, or radicals cm−3 and cm−3molecule−1sec−1, respectively.
37.
R. B.
Badachhape
,
P.
Kamarchik
,
A. P.
Conroy
,
G. P.
Glass
, and
J. L.
Margrave
,
Int. J. Chem. Kinet.
8
,
23
(
1976
).
38.
W.
Hack
,
H. Gg.
Wagner
, and
K.
Hoyermann
,
Ber. Bunsenges. Phys. Chem.
82
,
713
(
1978
).
39.
W.
Hack
,
A. W.
Preuss
,
H. Gg.
Wagner
, and
K.
Hoyermann
,
Ber. Bunsenges. Phys. Chem.
83
,
212
(
1979
).
40.
M. A. A.
Clyne
and
B. A.
Thrush
,
Proc. R. Soc. London Ser. A
275
,
559
(
1963
).
41.
A. A.
Westenberg
and
N.
deHaas
,
J. Phys. Chem.
76
,
1586
(
1972
).
42.
J. G.
Anderson
and
F.
Kaufman
,
Chem. Phys. Lett.
19
,
483
(
1973
).
43.
A. P.
Force
and
J. R.
Wiesenfeld
,
J. Chem. Phys.
74
,
1718
(
1981
).
44.
V. I.
Krassovsky
,
N. N.
Shefov
, and
V. I.
Yarin
,
Planet. Space Sci.
9
,
883
(
1962
).
45.
B. A.
Blackwell
,
J. C.
Polanyi
, and
J. J.
Sloan
,
Chem. Phys.
24
,
25
(
1977
).
46.
G. C.
Light
,
J. Chem. Phys.
68
,
2831
(
1978
).
47.
P. J. Robinson and K. A. Holbrook, Unimolecular Reactions (Wiley‐Interscience, New York, 1972).
48.
D. L.
Bunker
,
J. Chem. Phys.
40
,
1946
(
1964
).
49.
R. J.
Cvetanovic
,
R. P.
Overend
, and
G.
Paraskevopoulos
,
Int. J. Chem. Kinet. Symp.
1
,
249
(
1975
);
R. J.
Cvetanovic
and
D. L.
Singleton
,
Int. J. Chem. Kinet.
9
,
481
,
1007
(
1977
);
R. J.
Cvetanovic
,
D. L.
Singleton
, and
G.
Paraskevopoulos
,
J. Phys. Chem.
83
,
50
(
1979
), and references therein.
50.
P. R. Bevington, Data Reduction and Error Analysis for the Physical Sciences (McGraw‐Hill, New York, 1969), and references therein.
51.
E. M. Pugh and G. H. Winslow, The Analysis of Physical Measurements (Addison‐Wesley, Reading, Mass., 1966), and references therein.
This content is only available via PDF.
You do not currently have access to this content.