Non-equilibrium kinetics of bimolecular exchange reactions. Part 2.—Improved formalism and applications to H + H2→ H2+ H and its isotopic variants

1991 ◽  
Vol 87 (2) ◽  
pp. 229-239 ◽  
Author(s):  
Carol Bowes ◽  
Negin Mina ◽  
Heshel Teitelbaum
1994 ◽  
Vol 72 (3) ◽  
pp. 714-720
Author(s):  
Chris Carruthers ◽  
Heshel Teitelbaum

The master equation is solved numerically for the time dependence of the vibrational level populations of HCl (treated as a simple harmonic oscillator) during the bimolecular exchange reaction, Br + HCl → HBr + Cl, taking into account the competition between reaction and vibrational equilibration subject to Landau–Teller T–V excitation. Strong deviations from Boltzmann distributions are found. A wide range of reactant concentrations, diluent concentrations and temperatures were explored. It was found that no significant reaction occurs before the establishment of a steady vibrational population distribution, confirming that the rate coefficient for non-equilibrium bimolecular exchange reactions can be determined from a simple analytical steady state treatment (J. Chem. Soc. Faraday Trans. 87, 229 (1991)). The rate of an isolated elementary bimolecular reaction, A + BC → AB + C, under non-equilibrium conditions can deviate seriously from the standard expression, Keq [A][BC], and is better given by the law[Formula: see text]where [R] is the concentration of the collisional equilibrator, R, and a and g are constants depending only on temperature. This generalized rate law describes not only the initial rate but also the rate all the way up to completion, in the absence of the reverse reaction.


2018 ◽  
Vol 9 (23) ◽  
pp. 6750-6754 ◽  
Author(s):  
Alessandro Greco ◽  
Alexander Hinderhofer ◽  
M. Ibrahim Dar ◽  
Neha Arora ◽  
Jan Hagenlocher ◽  
...  

1977 ◽  
Vol 21 ◽  
pp. 209-215 ◽  
Author(s):  
D.C. Weatherburn ◽  
D.C. Weatherburn

2006 ◽  
Vol 70 (18) ◽  
pp. A53
Author(s):  
J.R. Black ◽  
M. Nyman ◽  
W.H. Casey

Earlier work from this laboratory has concerned the possible use of phosphorus n.m.r. as a method to monitor, in a non-invasive manner, the biochemical state of the perfused heart as a function of its mechanical performance. We showed that a simulated coronary infarction could be detected by 31 P n.m.r. (Hollis et al 1978 a and that hypothermia and KC1 arrest could preserve the pH and the ATP levels at more nearly normal values than in a non-arrested heart during long periods (40 min) of ischaemia (Hollis et al . 1978 b ).More recently it was shown that multiple doses of KC1, given at intervals, were more effective in this respect than was a single dose (Flaherty et al . 1979). These studies essentially followed the kinetics of transitions of the heart between two or more distinct physiological states (i.e. normoxic and ischaemic, with or without KC1 arrest) by observation of the 31 P n.m.r. spectra at various time intervals over periods of up to 1 h. As described in detail and demonstrated in Dr Truman Brown’s contribution to these discussions, the rates of chemical exchange reactions occurring in a steady state can be measured by the techniques of saturation transfer in various biological systems, including perfused hearts.


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