Kinetics of mechanochemical transformations

Carta, Maria; Colacino, Evelina; Delogu, Francesco; Porcheddu, Andrea

doi:10.1039/d0cp01658f

Cited by 44 publications

(44 citation statements)

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“…16−18 In recent years, different phenomenological models have been applied to ball mill reactions to describe the apparent kinetics of mechanochemical transformations. 19,20 In their principles these approaches take into account the very efficient stirring of the powder in the milling vessel leading to a global chemical homogeneity. However, depending on the critical loading conditions (CLCs), the activation of the transformation occurs in a small fraction of the powder which is trapped in the colliding zone of the milling media.…”

Section: Introductionmentioning

confidence: 99%

Elucidation of the Diels–Alder Reaction Kinetics between Diphenylfulvene and Maleimide by Mechanochemistry and in Solution

Gonnet

Chamayou

André-Barrès

et al. 2021

ACS Sustainable Chem. Eng.

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The Diels−Alder reaction kinetics between diphenylfulvene and maleimide using mechanochemistry and in liquid state is described. This reaction was carried out in solid state using a modified vibratory ball-mill with temperature control and in solution with toluene as solvent. The effect of temperature, ball mass, material, additives, and aging reaction were studied. We reported for the first time the kinetics of a mechanochemical reaction depending on the ratio ball mass/mass of the reagent. A new kinetic model has been established that corresponds well to our experimental data and allows an estimation of the global activation energy. In solution, the retro Diels−Alder reaction was observed. The reaction was second order for the formation of endo and exo and first order for the retro Diels−Alder reaction. The grinding method shows many advantages compared to solution: shorter reaction time, total reaction, and better selectivity.

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Section: Introductionmentioning

confidence: 99%

Elucidation of the Diels–Alder Reaction Kinetics between Diphenylfulvene and Maleimide by Mechanochemistry and in Solution

Gonnet

Chamayou

André-Barrès

et al. 2021

ACS Sustainable Chem. Eng.

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“…10,11 Following his work, we anticipate a wider use of in situ monitoring and kinetic modelling of mechanochemical processes, in particular since both methodologies are now described in technical detail. 29,35,36 Finally, we note that the herein studied trimerisation of Ni(dbm)2 could serve as a model reaction, instead of self-sustained reactions, 24,37 for comparing energy effects of different ball mills.…”

Section: Discussionmentioning

confidence: 99%

“…27,28 The reactant and the product are both stable solids and the reaction mixture is throughout milling in the form of a free-flowing powder enabling reaction monitoring by in situ Raman spectroscopy. Kinetic profiles were described by a model that accounts for the statistical nature of ball milling, 29,30 and the kinetic modelling was supported by numerical simulations of the milling process.…”

Section: Introductionmentioning

confidence: 99%

Mechanochemical reaction kinetics scales linearly with impact energy

Vugrin

Carta

Lukin

et al. 2022

Preprint

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Inelastic collisions of the milling media in ball milling provide energy to the reaction mixture required for a chemical transformations. However, movement of the milling media results also in physical mixing of reactants, which too may enable a chemical reaction. Separating the two contributions is challenging and gaining a direct insight into the purely mechanochemically driven reactivity is accordingly hindered. Here, we have applied in situ reaction monitoring by Raman spectroscopy to a suitable, purely mechanically activated, chemical reaction and combined kinetic analysis with numerical simulations to access experimentally unattainable milling parameters. The breadth of milling conditions allow us to establish a linear relationship between the reaction rate and the energy dose received by the sample. Consequently, different kinetic profiles in time scale to the same profile when plotted against the energy dose, which increases with the ball mass, the average ball velocity and the frequency of impacts, but it decreases with the hardness of the milling media due to more elastic collisions. The fundamental relationship between kinetics and energy input provides the basis for planning and optimisation of mechanochemical reactions and is essential for transferability of mechanochemical reactions across different milling platforms.

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“…Specifically, 𝑘 measures the volume fraction of powder that is processed effectively per unit time. 42 The intermediate volume fraction can be described by the equation 2: 3 3! + (𝑘𝑡) 4 4!…”

Section: Investigation Of the Kf-3cr By In Situ Raman Spectroscopymentioning

confidence: 99%

Kabachnik–Fields Reaction by Mechanochemistry: New Horizons from Old Methods

Fiore

Sović

Lukin

et al. 2020

ACS Sustainable Chem. Eng.

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-Aminophosphonates are an important class of biologically active compounds, attracting considerable attention in medicinal chemistry, by inhibiting enzymes involved in amino acid metabolism. Herein, the Kabachnik-Fields domino reaction was investigated by mechanochemistry for the first-time preparation of -aminophosphonate derivatives in high yields and with full selectivity, outperforming comparable solution procedures. The reaction is a Lewis acid-catalysed process occurring however without the addition of any external catalyst, but occurring on the surface of the zirconium oxide used as the milling media. The mechanism of the mechanochemical reaction was also investigated by in situ Raman spectroscopy, the kinetic behavior was disclosed. The solid-state structures of two representative compounds have been determined by single-crystal X-ray diffractions.

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Kinetics of mechanochemical transformations

Abstract:
To help understanding the mechanisms underlying mechanochemical transformations, we propose a kinetic model that relates macroscopic and microscopic scales while accounting for the statistical nature of the mechanical processing of powder.

Cited by 44 publications

References 50 publications

Elucidation of the Diels–Alder Reaction Kinetics between Diphenylfulvene and Maleimide by Mechanochemistry and in Solution

Elucidation of the Diels–Alder Reaction Kinetics between Diphenylfulvene and Maleimide by Mechanochemistry and in Solution

Mechanochemical reaction kinetics scales linearly with impact energy

Kabachnik–Fields Reaction by Mechanochemistry: New Horizons from Old Methods

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Kinetics of mechanochemical transformations

Abstract: To help understanding the mechanisms underlying mechanochemical transformations, we propose a kinetic model that relates macroscopic and microscopic scales while accounting for the statistical nature of the mechanical processing of powder.

Cited by 44 publications

References 50 publications

Elucidation of the Diels–Alder Reaction Kinetics between Diphenylfulvene and Maleimide by Mechanochemistry and in Solution

Elucidation of the Diels–Alder Reaction Kinetics between Diphenylfulvene and Maleimide by Mechanochemistry and in Solution

Mechanochemical reaction kinetics scales linearly with impact energy

Kabachnik–Fields Reaction by Mechanochemistry: New Horizons from Old Methods

Contact Info

Product

Resources

About

Abstract:
To help understanding the mechanisms underlying mechanochemical transformations, we propose a kinetic model that relates macroscopic and microscopic scales while accounting for the statistical nature of the mechanical processing of powder.