Simple Test of Unimolecular Reaction Theory

1967 ◽  
Vol 46 (11) ◽  
pp. 4504-4508 ◽  
Author(s):  
Richard K. Lyon
Keyword(s):  
Unimolecular Reaction ◽  
Simple Test ◽  
Reaction Theory

On the Unimolecular Decomposition of the tert-Butoxy Radical

1973 ◽  
Vol 51 (13) ◽  
pp. 2138-2140 ◽  
Author(s):  
C. K. Yip ◽  
H. O. Pritchard
Keyword(s):  
Pressure Dependence ◽  
Unimolecular Reaction ◽  
Unimolecular Decomposition ◽  
Reaction Theory ◽  
Butoxy Radical

It is argued that a large apparent pressure dependence in the rate of decomposition of the tert-butoxy radical should not be interpreted in terms of unimolecular reaction theory; the effect is probably heterogeneous in origin.

The commutative property of strong-transition rate matrices

1979 ◽  
Vol 57 (21) ◽  
pp. 2793-2797 ◽  
Author(s):  
Huw O. Pritchard ◽  
Arunachalam Lakshmi
Keyword(s):  
Transition Rate ◽  
Transition Probabilities ◽  
Boltzmann Distribution ◽  
Unimolecular Reaction ◽  
Infinite Time ◽  
Relaxation Matrix ◽  
Reaction Theory ◽  
Strong Transition ◽  
Commutative Property

The (n − 1)-fold degenerate set of transition probabilities used in our recent reformulation of unimolecular reaction theory is operationally equivalent to the set of effective strong-transition probabilities introduced recently by Nordholm. We have found that the relaxation matrix corresponding to these transition probabilities commutes with any other relaxation matrix which will drive the same system to a Boltzmann distribution at infinite time. Some useful results stemming from this commutative property are presented; we expect that these results will help to clarify further the nature of the assumptions underlying strong- and effective strong-collision theories.

Decomposition of Activated sec‐Butyl Radicals from Different Sources and Unimolecular Reaction Theory

1960 ◽  
Vol 33 (4) ◽  
pp. 1271-1272 ◽  
Author(s):  
R. E. Harrington ◽  
B. S. Rabinovitch ◽  
H. M. Frey
Keyword(s):  
Unimolecular Reaction ◽  
Reaction Theory ◽  
Different Sources

Nonequilibrium Effects in Unimolecular Reaction Theory

1966 ◽  
Vol 45 (11) ◽  
pp. 4280-4288 ◽  
Author(s):  
W. G. Valance ◽  
E. W. Schlag
Keyword(s):  
Unimolecular Reaction ◽  
Reaction Theory ◽  
Nonequilibrium Effects

An alternative view of unimolecular reaction theory

1977 ◽  
Vol 55 (2) ◽  
pp. 284-292 ◽  
Author(s):  
Huw Owen Pritchard
Keyword(s):  
Alternative View ◽  
Unimolecular Reaction ◽  
Matrix Elements ◽  
Stochastic Matrices ◽  
Total Rate ◽  
Primitive Form ◽  
Pressure Limit ◽  
The Matrix ◽  
Reaction Theory ◽  
Comparison Of The Results

A primitive form of unimolecular reaction theory is constructed, based on the master equation. Application of the theory depends upon the way in which eigenvalues of large stochastic matrices behave as certain of the matrix elements are varied. Some of the required eigenvalue properties have been deduced by numerical experiment, and others are available from earlier work on diatomic dissociation reactions. Comparison of the results from this primitive approach with those of existing theories of unimolecular reactions suggests some reinterpretation of parameters used in those theories: most interestingly, the number of effective oscillators occurring in Kassel theory (or its Slater-theory equivalent) appears to be the ratio, at infinite pressure, of the total rate to the rate of the only reaction channel which survives at the low-pressure limit.

A Simple Test for Urine Bilirubin

1953 ◽  
Vol 24 (3) ◽  
pp. 414-421 ◽  
Author(s):  
Alfred H. Free ◽  
Helen M. Free
Keyword(s):  
Simple Test
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