Varying the activation parameters as a method of determining whether there is an isokinetic relationship among the bimolecular nucleophilic reactions of benzene derivatives in solution

Vlasov, V. M.

doi:10.1007/s00706-012-0765-x

Cited by 4 publications

(3 citation statements)

References 48 publications

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“…Effectively, it has been observed in Figure that an enthalpy–entropy compensation effect is found even when there is no real correlation between the activation parameters, provided that the accidental errors associated with the determination of the rate constants are high enough. Although some authors have published useful tools for this purpose, ,, the search for a different alternative, potentially providing further quantitative information, seems attractive enough. Thus, the following goal of this research will be the elaboration of a test capable of discerning whether a certain activation enthalpy–entropy linear relationship found in the laboratory can be explained by the occurrence of experimental errors or not.…”

Section: P-testmentioning

confidence: 99%

“…Several methods have been previously proposed to discriminate error-induced compensation plots from those with a real physical origin. ,,,,, These methods can be regarded as complementary, often leading to coherent results. However, the one now presented ( p -test) might be more intuitive, because it yields a parameter with a direct physical interpretation: the probability of an isokinetic relationship found for a particular homologous reaction series being explainable as a consequence of random experimental errors.…”

Section: P-testmentioning

confidence: 99%

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Enthalpy–Entropy Compensation Effect in Chemical Kinetics and Experimental Errors: A Numerical Simulation Approach

Perez‐Benito

Mulero-Raichs

2016

J. Phys. Chem. A

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Many kinetic studies concerning homologous reaction series report the existence of an activation enthalpy-entropy linear correlation (compensation plot), its slope being the temperature at which all the members of the series have the same rate constant (isokinetic temperature). Unfortunately, it has been demonstrated by statistical methods that the experimental errors associated with the activation enthalpy and entropy are mutually interdependent. Therefore, the possibility that some of those correlations might be caused by accidental errors has been explored by numerical simulations. As a result of this study, a computer program has been developed to evaluate the probability that experimental errors might lead to a linear compensation plot parting from an initial randomly scattered set of activation parameters (p-test). Application of this program to kinetic data for 100 homologous reaction series extracted from bibliographic sources has allowed concluding that most of the reported compensation plots can hardly be explained by the accumulation of experimental errors, thus requiring the existence of a previously existing, physically meaningful correlation.

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Section: P-testmentioning

confidence: 99%

Section: P-testmentioning

confidence: 99%

Enthalpy–Entropy Compensation Effect in Chemical Kinetics and Experimental Errors: A Numerical Simulation Approach

Perez‐Benito

Mulero-Raichs

2016

J. Phys. Chem. A

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“…The lines II and III from Figure 1 combine a relatively fast reactions [50,[53][54][55][56][57][58][59][60][61][62][63][64][65][66][67] and the compensation relationships for these lines are tested at a confidence level of >95% [27,43]. The slopes of the lines II and III correspond to compensation temperatures Tcomp equaling 380 and 370 K, respectively.…”

Section: Reaction Constants δδH ≠ and δδS ≠mentioning

confidence: 99%

Activation parameter changes as a mechanistic tool in SN2 reactions in solution

Vlasov

2015

Eur. J. Chem.

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Recent applications of activation parameters variation approach to the elucidation of SN2 reaction mechanisms have led to further clarifications of structures of transition states involved in the concerted reaction pathway. SN2 reactions in solution are reviewed with special emphasis of activation parameter variation ΔX ≠ (X = H, S and G) with substituents in the nucleophile, leaving and nonleaving groups applying linear free energy relationships in order to evaluate the resultant δΔX ≠ reaction constants. The use of internal enthalpy reaction constants δΔH ≠ int as a mechanistic tool is stressed when the structure of transition state in SN2 reaction is changed. Variations of the activation parameters in SN2 reactions and their mechanisms were analyzed.

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Aromatic Substitution

Crampton¹

2016

Organic Reaction Mechanisms · 2013

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Varying the activation parameters as a method of determining whether there is an isokinetic relationship among the bimolecular nucleophilic reactions of benzene derivatives in solution

Cited by 4 publications

References 48 publications

Enthalpy–Entropy Compensation Effect in Chemical Kinetics and Experimental Errors: A Numerical Simulation Approach

Enthalpy–Entropy Compensation Effect in Chemical Kinetics and Experimental Errors: A Numerical Simulation Approach

Activation parameter changes as a mechanistic tool in SN2 reactions in solution

Aromatic Substitution

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