(CO2)‡ and (CO3)‡ structures were proposed as the activated complex of the rate determining and isotope fractionation governing step in the catalytic oxidation of CO over NiO catalyst. Following Bigeleisen’s formalism, the theoretical rate constant ratios for 13C and 14C substitution were calculated and compared with the experimental values. Computational analysis confirmed the (CO2)‡ activated complex and pointed out that the (CO3)‡ activated complex could not explain the experimetal results.
REFERENCES
1.
2.
See references in Ref. 1.
3.
I. Kobal, M. Senegačnik, and B. Barlič, 4th Natl. Conf. Pure & Appl. Phys. Chem. Bucharest, Romania, 1974.
4.
5.
6.
7.
J. Bigeleisen, Proc. Symp. Iosotpe Mass Eff. in Chem. & Biol., Vienna 1963 (Butterworth, London, 1964).
8.
9.
10.
W. A. Van Hook, Isotope Effects in Chemical Reactions, edited by C. J. Collins and N. S. Bowman (Van Nostrand Reinhold, New York, 1970).
11.
L. Melander, Isotope Effects on Reaction Rates (Ronald, New York, 1960).
12.
S. Glasstone, K. Laidler, and H. Eyring, The Theory of Rate Processes (McGraw Hill, New York, 1941).
13.
K. Laidler, Chemical Kinetics (McGraw Hill, New York, 1965).
14.
15.
J. S.
Shapiro
and R. E.
Weston
, Jr., J. Phys. Chem.
76
, 1669
(1972
).16.
E. B. Wilson, J. C. Decius, and P. C. Cross, Molecular Vibrations (McGraw Hill, New York, 1965).
17.
P. Guns, Vibrating Molecules (Chapman & Hall, London, 1971).
18.
K. Nakamoto, Infrared Spectra of Inorganic and Coordination Compounds (Wiley, New York, 1963).
19.
N.‐A.
Bergman
, W. H.
Saunders
, Jr., and L.
Melander
, Acta Chem. Scand.
28
, 1130
(1972
).20.
B. Barlic, M.S. thesis, University of Ljubljana, 1973.
21.
J. Bigeleisen, Discussion after the lecture “Present status in the isotope effect research” held at J. Stefan Institute, Univ. of Ljubljana, Yugoslavia, 1973.
22.
S. Roginskii, Teoretischeske osnovi izotopnih metodov izucheniya khimicheskih reakcii, Akademija Nauk SSR, 1956.
23.
M. Senegačnik, These, CEA Report no 726, Paris 1957.
24.
J. A.
Ladd
, W. J.
Orville‐Thomas
, and B. C.
Cox
, Spectrochim. Acta
20
, 1771
(1964
).25.
T. T.‐S.
Huang
, W. J.
Kass
, W. E.
Buddenbaum
, and P. E.
Yankwich
, J. Phys. Chem.
72
, 4431
(1968
).26.
27.
28.
29.
M. Senegačnik, S. Polič, and I. Kobal, J. Stefan Institute Report DP‐972 (1975).
30.
G. Herzberg, Molecular Spectra and Molecular Structure II, Infrared and Raman Spectra of Polyatomic Molecules (Van Nostrand, New York, 1949).
31.
32.
Z.
Bilkadi
, M. W.
Lee
, and J.
Bigeleisen
, J. Chem. Phys.
62
, 2087
(1975
).33.
A. Ažman (private communication).
34.
35.
36.
37.
38.
N. S.
Dalal
, C. A.
McDowell
, and J. M.
Park
, J. Chem. Phys.
63
, 1856
(1975
).39.
40.
41.
42.
K.
Kuchynka
, K.
Klier
, Collect. Czech. Chem. Commun.
28
, 148
(1963
).43.
44.
J. H.
Keller
, P. E.
Yankwich
, J. Am. Chem. Soc.
95
, 4811
, 7968
(1973
).45.
This content is only available via PDF.
© 1978 American Institute of Physics.
1978
American Institute of Physics
You do not currently have access to this content.
