High‐pressure mechanistic delineation based on activation volumes

Jenner, G.

doi:10.1002/poc.458

Cited by 42 publications

(27 citation statements)

References 30 publications

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“…33 A linear fit to the data yields ∆V ≠ =-2.3 Å 3 ±0.2 Å 3 . The activation volume can be associated with the volume change of the transition state, which in our case must be smaller than that of the reactant D-9TBA.…”

Section: Resultsmentioning

confidence: 95%

Pressure Dependence of the Forward and Backward Rates of 9-tert-Butylanthracene Dewar Isomerization

et al. 2014

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9-tert-Butylanthracene undergoes a photochemical reaction to form its strained Dewar isomer, which thermally back-reacts to reform the original molecule. When 9-tert-butylanthracene is dissolved in a polymer host, we find that both the forward and reverse isomerization rates are pressure-dependent. The forward photoreaction rate, which reflects the sum of contributions from photoperoxidation and Dewar isomerization, decreases by a factor of 1000 at high pressure (1.5 GPa). The back-reaction rate, on the other hand, increases by a factor of ∼3 at high pressure. Despite being highly strained and higher volume, the back-reaction reaction rate of the Dewar isomer is at least 100× less sensitive to pressure than that of the bi(anthracene-9,10-dimethylene) photodimer studied previously by our group. These results suggest that the high pressure sensitivity of the bi(anthracene-9,10-dimethylene) photodimer reaction is not just due to the presence of strained four-membered rings but instead relies on the unique molecular geometry of this molecule.

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Section: Resultsmentioning

confidence: 95%

Pressure Dependence of the Forward and Backward Rates of 9-tert-Butylanthracene Dewar Isomerization

et al. 2014

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“…In a similar manner as given for the temperature, an increase of the kinetic constant can be reached when increasing the pressure, if steric effects are given during a reaction [127][128][129]. While such effects may not be strong and thus overlooked at normal pressures, a significant increase in pressure > 100 bar can reveal such effect for many reactions, but this could hardly be exploited in the laboratory, as autoclave operation is complex, requires larger volumes, and needs longer reaction times when compared to microreactors.…”

Section: Pressure Effectsmentioning

confidence: 90%

Potential Analysis of Smart Flow Processing and Micro Process Technology for Fastening Process Development: Use of Chemistry and Process Design as Intensification Fields

et al. 2012

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Flow processes with microstructured reactors allow paradigm changes in process development and thus can enable a faster development time to the final production plant. They do this by exploiting similarity effects along the development chain (modularity) and intensification. The final result can be a (significantly) reduced number of apparatus in the plant, a (significantly) reduced apparatus size, and a higher predictability in the scale-out of the apparatus. So far, this was mainly achieved via transport intensification given in microstructured reactorsimproved mixing and heat transfer which increase productivity and possibly improve selectivity. A more new idea is chemical intensification through deliberate use of harsh chemistries at unusual (high) pressure, temperature, concentration, and reaction environment which again increases productivity. A very new idea is the process design intensification -the reaction-maximized flow processes need less separation expenditure and the small unit size together with the high degree in functionality gives large potential for system integration. Both means change and simplify the process scheme totally which can lead to a reduced number of apparatus and has impact on predictability. The modular nature of the small flow units allow an easy implementation to modern modular plant environments (Future Factories) which enables to perform all the testing cycles (lab, pilot, production) in one plant environment; an example are here container plants. All these measures have large potential for (much) decreased overall development time.

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“…[48][49][50][51][52][64][65][66][67][68][69][70][71][72][73] Technical development recently has revolved mostly around improvements, often incremental, in aspects such as sensitivity, detection range, resolution, and particularly in data acquisition and processing. Hence, a total survey of all the variations of pressure cells, their incorporation into appropriate instruments, and their method of operation will not be repeated here.…”

Section: General Considerationsmentioning

confidence: 99%

Application of High Pressure in the Elucidation of Inorganic and Bioinorganic Reaction Mechanisms

Hubbard¹,

Eldik²

2010

Physical Inorganic Chemistry

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High‐pressure mechanistic delineation based on activation volumes

Cited by 42 publications

References 30 publications

Pressure Dependence of the Forward and Backward Rates of 9-tert-Butylanthracene Dewar Isomerization

Pressure Dependence of the Forward and Backward Rates of 9-tert-Butylanthracene Dewar Isomerization

Potential Analysis of Smart Flow Processing and Micro Process Technology for Fastening Process Development: Use of Chemistry and Process Design as Intensification Fields

Application of High Pressure in the Elucidation of Inorganic and Bioinorganic Reaction Mechanisms

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