Application of high pressure kinetic techniques to mechanistic studies in coordination chemistry

Kotowski, M.; Eldik, Rudi van

doi:10.1016/0010-8545(89)80011-6

Cited by 40 publications

(12 citation statements)

References 86 publications

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“…[15]- [17] or [19] are elusive, as one must choose a system for which AVIlS and A V~~~ are known and accountable for theoretically (Table 2), and for which k,, and AV,: are measurable. The problem is usually that the highpressure techniques (48,49) available for the measurement of k,,, notably stopped-flow spectrophotometry, cannot produce reliable rate constants >lo5 L mol-' s-', so that eq. [18] limits the choice of participating couples to ones with fairly slow self-exchange rates and a rather small AE.…”

Section: Swaddlementioning

confidence: 99%

Reflections on the outer-sphere mechanism of electron transfer

Swaddle¹

1996

Can. J. Chem.

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Abstract:The quantitative efficacy of the Stranks-Marcus-Hush theory of volumes of activation A v~ for outer-sphere electron transfer between metal complexes in solution is assessed. The theory predicts A v S accurately for several couples in aqueous solution, but is satisfactory for polar nonaqueous solvents only at pressures of ca. 100 MPa and above, and accuracy is not improved when the molecular nature of the solvent is allowed for through the Mean Spherical Approximation approach. At low pressures, the calculations become numerically unstable when the isothermal compressibility of the solvent is high and its relative permittivity is low, particularly for the more highly charged couples. For aqueous systems, departures from the predicted A v t afford insights into the role of the counterions, the incursion of inner-sphere pathways, the enhanced reactivity of CO""" cage complexes relative to conventional chelates, and the question of "spin forbiddenness" of electron transfer processes that involve a large change in spin multiplicity.Key words: redox kinetics, inorganic reaction mechanisms, pressure effects, Marcus-Hush theory, activation volumes. prkdites fournissent des renseignements sur le r6le des contre-ions, sur les incursions de voies impliquant les sphkres internes, I'augmentation de la rCactivitC des complexes de cage du CO""" par rapport aux chClates conventionnels et la question de l'<

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Section: Swaddlementioning

confidence: 99%

Reflections on the outer-sphere mechanism of electron transfer

Swaddle¹

1996

Can. J. Chem.

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“…Commonly used equipment for high-pressure chemistry are autoclaves combined with optical detection techniques [3] or NMR-probes [4]. High-pressure chemistry requires specialized, complicated and expensive equipment due to the strict safety precautions.…”

Section: Introductionmentioning

confidence: 99%

Fabrication, mechanical testing and application of high-pressure glass microreactor chips

Tiggelaar¹,

Benito‐Lopez²,

Hermes³

et al. 2007

Chemical Engineering Journal

115

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The design, fabrication and high-pressure performance of several in-plane fiber-based interface geometries to microreactor chips for highpressure chemistry are discussed, and an application is presented. The main investigated design parameters are the geometry of the inlet/outlet structure, the manner in which top and bottom wafer are bonded and the way the inlets/outlets turn over into the microfluidic channels.Destructive pressure experiments with H 2 O and liquid CO 2 showed that the maximum pressure that the proposed inlet/outlet structures can withstand is in the range of 180-690 bar. The optimal geometry for high-pressure microreactor chips is a tubular structure that is etched with hydrofluoric acid (HF) and suitable for fibers with a diameter of 110 m. These inlets/outlets can withstand pressures up to 690 bar. On the other hand, small powderblasted inlets/outlets that are smoothened with HF and with a sharp transition towards the flow channels are adequate for working pressures up to 300 bar.Microreactor chips with tubular inlet/outlet geometries were used for studying the formation of the carbamic acid of N-benzylmethylamine and CO 2 . These chips could be used for pressures up to 400 bar without problems/failure, thereby showing that these micromachined microreactor chips are attractive tools for performing high-pressure chemistry in a fast and safe way.

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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%

“…Surveys have been reported several times in recent years. [64][65][66][67][68][69][70][71][72][73] However, some of the guiding principles and general approach in successful practice in high-pressure kinetics measurements, independent of the particular method or instrument, will be covered. Consideration of various properties, many of them obvious, and conditions of reactants and solvents for suitable design of experiments will also be noted.…”

Section: General Considerationsmentioning

confidence: 99%