Reply to the ‘Comment on “The thermal unimolecular decomposition of HCO: effects of state specific rate constants on the thermal rate constant” ’ by L. N. Krasnoperov, Phys. Chem. Chem. Phys., 2005,7, DOI: 10.1039/b418813f

2005 ◽  
Vol 7 (9) ◽  
pp. 2077-2079 ◽  
Author(s):  
H. Hippler ◽  
N. Krasteva ◽  
F. Striebel
Keyword(s):  
Rate Constant ◽  
Rate Constants ◽  
Chem Phys ◽  
Specific Rate ◽  
Unimolecular Decomposition ◽  
Phys Chem Chem Phys ◽  
Thermal Rate Constant

Anharmonic effect of the decomposition reaction of the CF3CCl2O radical

2012 ◽  
Vol 90 (2) ◽  
pp. 186-194 ◽  
Author(s):  
Qian Li ◽  
Wenwen Xia ◽  
Li Yao ◽  
Ying Shao
Keyword(s):  
Rate Constant ◽  
Rate Constants ◽  
Decomposition Reaction ◽  
Unimolecular Decomposition ◽  
Anharmonic Effect ◽  
Canonical Systems ◽  
Bond Scission

The rate constant of the unimolecular decomposition reaction of the CF3CCl2O radical was calculated by using the method proposed by Yao and Lin (YL method). Two important channels of decomposition occurring via C–C and C–Cl bond scission were investigated. The results show that C–Cl bond scission is the dominant channel during the decomposition of the CF3CCl2O radical. Especially, the reasonable anharmonic effect on the decomposition reaction was investigated. The results show that the harmonic rate constants are higher than those of the anharmonic case in both microcanonical and canonical systems. The anharmonic effect is more evident with increasing energy.

Kinetics and mechanism of the oxidation of oxalate ion by tris(acetylacetonato)-manganese(III) and its hydrolytic derivatives in aqueous perchlorate media

1993 ◽  
Vol 71 (12) ◽  
pp. 2155-2159 ◽  
Author(s):  
Subrata Mukhopadhyay ◽  
Swapan Chaudhuri ◽  
Rina Das ◽  
Rupendranath Banerjee
Keyword(s):  
Free Radicals ◽  
Rate Constant ◽  
Decomposition Rate ◽  
Rate Constants ◽  
Kinetics And Mechanism ◽  
Unimolecular Decomposition ◽  
Decomposition Rate Constant ◽  
Mixed Complexes ◽  
Ph Range ◽  
Oxalate Ion

In the pH range 6.6–8.6, [MnL2(H2O)2]+ and [MnL2(H2O)(OH)] (HL = acetylacetone) oxidize oxalate ion (ox2−) to CO2 through the inner-sphere intermediates [MnL2(ox)]− and [MnL2(OH)(ox′)]2−, where ox′ is a half-bonded (unidentate) oxalate ion. Their rate constants of decomposition are 1.0 × 10−4 s−1 and 11.2 × 10−2 M−1 s−1 at 30 °C and at I = 1.0 M (NaClO4). Decomposition of these mixed complexes produces free radicals, presumably CO2−, which is further oxidized to CO2 by another Mn(III) in a fast step. At pH 4.2, [Mn(ox)3]3− is produced quantitatively when [ox]0 ≥ 0.12 M, which has been characterized spectrally, and its unimolecular decomposition rate constant k (= 2.7 × 10−4s−1 at 30 °C and I = 1.0 M) compares well with that reported earlier (2.44 × 10−4 s−1 at 25 °C and I = 1.0 M).

scholarly journals The Alkaline solvolysis of allyl bromide in alcohol-water solvents

2021 ◽  
Author(s):  
◽  
Valda Hilary Donald
Keyword(s):  
Nucleophilic Substitution ◽  
Rate Constant ◽  
Solvent Effects ◽  
Rate Constants ◽  
Allyl Bromide ◽  
Solvent Polarity ◽  
Specific Rate ◽  
Increase With Increase ◽  
Alcohol Water ◽  
The Individual

<p>The rate of the alkaline solvolysis of allyl bromide has been measured in various ethanol-water and methanol-water mixtures. This has been found to increase with increase in solvent polarity. An attempt was made to explain this behaviour in terms of partial ionisation of the substrate. It has been suggested that in nucleophilic substitution the individual specific rate constants for attack by alkoxide or hydroxide ions are a better indication of solvent effects than the apparent overall rate constant.</p>

Unimolecular decomposition of the n-C3H7 radical. Direct dynamics calculation of the thermal rate constant

2001 ◽  
Vol 3 (12) ◽  
pp. 2459-2466 ◽  
Author(s):  
Luminita C. Jitariu ◽  
Hong Wang ◽  
Ian H. Hillier ◽  
Michael J. Pilling
Keyword(s):  
Rate Constant ◽  
Unimolecular Decomposition ◽  
Direct Dynamics ◽  
Dynamics Calculation ◽  
Thermal Rate Constant

The kinetics of internal energy randomisation in thermal unimolecular reactions

1980 ◽  
Vol 58 (21) ◽  
pp. 2236-2245 ◽  
Author(s):  
Huw Owen Pritchard
Keyword(s):  
Internal Energy ◽  
Lower Limit ◽  
Rate Constant ◽  
Rate Constants ◽  
Rate Function ◽  
Second Order ◽  
Specific Rate ◽  
Unimolecular Reactions ◽  
Methyl Isocyanide ◽  
Kinetics Of

The aim of this paper is to present a minimal theory of thermal unimolecular reactions, including explicitly the kinetics of intramolecular randomisation processes. A quasi-diatomic model is formulated and, within the framework of the model, both first-and second-order randomisation processes among reactant and product states are examined.It is concluded that a vital mechanism for the intramolecular energy randomisation in thermal unimolecular reactions is a collisional one. On this assumption, a straightforward derivation of the Polanyi–Wigner specific rate function, as we have reinterpreted it, becomes possible.At the same time, anomalies in the fall-off curves for the thermal isomerisations of methyl isocyanide and ethyl isocyanide can be accounted for very simply: in the former case, values for both the first- and second-order randomisation rate constants can be derived, but in the latter case it is only possible to establish a lower limit for the second-order randomisation rate constant.

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