Determination of the reaction acceleration effect at an elevated hydrostatic pressure

Kornilov, Dmitry A.; Kiselev, V. D.; Konovalov, A. I.

doi:10.1007/s11172-017-1772-1

Cited by 7 publications

(5 citation statements)

References 10 publications

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“…Thus, the use of the ratio of the activation volume to the reaction volume of isopolar cycloaddition reactions in solution to determine the location of the transition state on the reaction coordinate is unsuitable, and also not always useful for establishing the mechanism of such reactions 45 . However, it is important to know the values of the activation volumes and reaction volumes for optimizing chemical processes occurring at high hydrostatic pressure 46 …”

Section: Resultsmentioning

confidence: 99%

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High pressure, temperature, and solvent effect on the Diels–Alder cycloaddition reaction between thiobenzophenone and cyclopentadiene

Kornilov

Kornilova

Shulyatiev

et al. 2023

Int J of Chemical Kinetics

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The data on high hydrostatic pressure, temperature, and solvent influence on the Diels–Alder reaction rate of thiobenzophenone with cyclopentadiene have been obtained. Activation enthalpies, entropies, volumes, and reaction volumes in several solvents have been determined. The activation entropies and volumes of the Diels–Alder reaction of thiobenzophenone with cyclopentadiene are close to the corresponding activation parameters of Diels–Alder reactions involving dienophiles with C=C and N=N bonds. The rate of thiobenzophenone‐cyclopentadiene reaction did not increase with increasing solvent polarity, which is also characteristic of other Diels–Alder reactions. The reaction of thiobenzophenone with cyclopentadiene is characterized by an “anomalous” ratio of the activation volume to the reaction volume ∆V≠/∆Vr‐n > 1. This can be explained by the less steric hindrances of transition‐state molecules toward the solvent, compared with adduct molecules. The activities of a number of dienophiles with C=C, C=S, and N=N bonds have been compared, and the factors determining their reactivity in Diels–Alder reactions have been established.

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Section: Resultsmentioning

confidence: 99%

“…45 However, it is important to know the values of the activation volumes and reaction volumes for optimizing chemical processes occurring at high hydrostatic pressure. 46…”

Section: Solventmentioning

confidence: 99%

High pressure, temperature, and solvent effect on the Diels–Alder cycloaddition reaction between thiobenzophenone and cyclopentadiene

Kornilov

Kornilova

Shulyatiev

et al. 2023

Int J of Chemical Kinetics

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“…The thin dashed green line is for the Kornilov et al . 62 moderate pressures approximation (Eq. (10b)).…”

Section: Resultsmentioning

confidence: 99%

“…Recently, Kornilov et al . 62 experimentally studied reaction rate constants for which the following relation was applied: = a ′ P + b ′ P 2 , for P < (220–300 MPa ). It can be linked to the simple approximation of the SB Eq.…”

Section: Resultsmentioning

confidence: 99%

Activation volume in superpressed glass-formers

Drozd-Rzoska

2019

Sci Rep

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In pressurized glass-forming systems, the apparent (changeable) activation volume Va(P) is the key property governing the previtreous behavior of the structural relaxation time (τ) or viscosity (η), following the Super-Barus behavior: , T = const. It is usually assumed that Va(P) = V#(P), where or . This report shows that Va(P) ≪ V#(P) for P → Pg, where Pg denotes the glass pressure, and the magnitude V#(P) is coupled to the pressure steepness index (the apparent fragility). V#(P) and Va(P) coincides only for the basic Barus dynamics, where Va(P) = Va = const in the given pressure domain, or for P → 0. The simple and non-biased way of determining Va(P) and the relation for its parameterization are proposed. The derived relation resembles Murnaghan - O’Connel equation, applied in deep Earth studies. It also offers a possibility of estimating the pressure and volume at the absolute stability limit. The application of the methodology is shown for diisobutyl phthalate (DIIP, low-molecular-weight liquid), isooctyloxycyanobiphenyl (8*OCB, liquid crystal) and bisphenol A/epichlorohydrin (EPON 828, epoxy resin), respectively.

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“…1). 5,6 The sensitivity of the kinetic response to pressure is quantified by the so-called volume of activation 7 (∆V ‡ ), as defined in (1), where ∆V ‡ represents the difference in volume between starting materials and the transition state. Ionogenic reactions are particularly strongly promoted by UHP as a result of electostriction 8 reducing the volume of the solvated species due to the attractive effect that developing charges exert on the solvent.…”

Section: Introductionmentioning

confidence: 99%