Measurements of vibrational energy transfer probabilities are presented for the temperature range 205–360 °K for HF–DF, HF–CO2, and DF–CO2 gas mixtures. The present results provide an accurate determination of the inverse temperature dependence of the energy transfer probabilities exhibited by these systems. Large deactivation effects caused by HF (DF) polymers were observed for temperatures below 220 °K.
REFERENCES
1.
2.
3.
4.
5.
6.
7.
8.
W. C.
Solomon
, J. A.
Blauer
, F. C.
Jaye
, and J. G.
Hnat
, Int. J. Chem. Kinet.
3
, 215
(1971
).9.
J. A.
Blauer
, W. C.
Solomon
, and T. W.
Owens
, Int. J. Chem. Kinet.
4
, 293
(1972
).10.
11.
12.
13.
L. S.
Blair
, W. D.
Breshears
, and G. L.
Schott
, J. Chem. Phys.
59
, 1582
(1973
).14.
15.
16.
17.
We are indebted to Dr. J. K. Hancock for suggesting this technique for temperature measurement.
18.
19.
20.
21.
22.
R. M.
Osgood
, Jr., A.
Javan
, and P. B.
Sackett
, Appl. Phys. Lett.
20
, 469
(1972
).23.
Data discussed in Ref. 24, below, indicate that HF is predominantly in the monomer form for temperatures above 200 °K for pressures of interest in the present experiments.
24.
J. N.
Maclean
, F. J. C.
Rossotti
, and H. S.
Rossotti
, J. Inorg. Nucl. Chem.
24
, 1549
(1962
).25.
26.
27.
28.
Presumably this correction would be a 19% reduction in the probabilities given in Fig. 7; however, since the apparatus of Ref. 6 was no longer in existence, the magnitude of this correction could not be directly verified.
29.
The use of very large assumed values of in calculations of the variation of relaxation rates with composition leads to curves which depart from the observed linear dependence of on The upper bounds on given in Table II represent values which would lead to nonlinear curves discernibly different from the experimental data.
30.
For further discussion of this point, see Ref. 1. The error bars of Fig. 12 represent limiting conceivable values of that would be consistent with the measured dependence of on for the fluorescence data.
31.
32.
33.
34.
D. R.
Yarkony
, S. V.
O’Neil
, H. F.
Schaefer
III, C. P.
Baskin
, and C. F.
Bender
, J. Chem. Phys.
60
, 855
(1974
).35.
J. K. Hancock (private communication, October 1974).
This content is only available via PDF.
© 1975 American Institute of Physics.
1975
American Institute of Physics
You do not currently have access to this content.