Solvent effects on reactions in supercritical fluids

Wu, Benjamin C.; Klein, Michael T.; Sandler, Stanley I.

doi:10.1021/ie00053a003

Cited by 72 publications

(66 citation statements)

References 42 publications

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“…Because these products appeared to be formed from the same or similar intermediates (pathways I-m and VT>, a favorable concentration dependence for the ring contraction of pathways I-m over the 1,5 H isomerization of pathway VI and other alternatives to ring contraction could explain this trend. One explanation could be caging effects, as had been proposed in the program's earliest study (7) and had been commonly considered in the chemical process industry (22).…”

Section: A Experimental Resultsmentioning

confidence: 99%

“…7, it was proposed that dimethylpentane developed from its corresponding MHL radical shown. The process by which the initial 6-member ring was converted to a 5-member ring was most apparently due to the phenomenon of caging, a phenomenon frequently discussed in the supercritical chemical process literature (22).…”

Section: B Review and Analysis Of Experimental Resultsmentioning

confidence: 99%

“…In order to estimate the effect of caging with respect to a chemical process, the general approach had been to apply transition state theory (22,25). What essentially had been considered in general transition state theory (25) would be determined by tire ratio of the collisional rate of formation of the new cyclohydrocarbon due to caging to the diffusion rate of the ß scission products "to get out of the cage".…”

Section: B Review and Analysis Of Experimental Resultsmentioning

confidence: 99%

“…where v is the collision frequency (sec*), d* the collision cross section, E the activation energy and D the mass diffusivity (cm7sec) (22). Essentially vd 2 is the pre-exponential kinetic A factor of the rate expression in the numerator.…”

Section: B Review and Analysis Of Experimental Resultsmentioning

confidence: 99%

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Fuels Combustion Research, Supercritical Fuel Pyrolysis

Glassman¹

1998

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Public reporting burden for this collection of information is estimated to average 1 hour per response, including the time for reviewing instructions, searching existing data sources, gathering and maintaining the data needed, and completing and reviewing this collection of information. Send comments regarding this burden estimate or any other aspect of this collection of information, including suggestions for reducing this burden to Department of Defense, Washington Headquarters Services, Directorate for Information Operations and Reports (0704-0188), 1215 Jefferson Davis Highway, Suite 1204, Arlington, VA 22202-4302. Respondents should be aware that notwithstanding any other provision of law, no person shall be subject to any penalty for failing to comply with a collection of information if it does not display a currently valid OMB control number. PLEASE DO NOT RETURN YOUR FORM TO THE ABOVE ADDRESS. REPORT DATE (DD-MM-YYYY) 2308/BX5f. WORK UNIT NUMBER PERFORMING ORGANIZATION NAME(S) AND ADDRESS(ES)Princeton University Department of Mechanical and Aerospace Engineering Princeton, NJ 08544 8. PERFORMING ORGANIZATION REPORT NUMBER SPONSORING / MONITORING AGENCY NAME(S) AND ADDRESS(ES)AFOSR/NA 110 Duncan Avenue, Room B115 Boiling AFB, DC 20332-8050 SPONSOR/MONITOR'S ACRONYM(S) SPONSOR/MONITOR'S REPORT NUMBER(S) DISTRIBUTION / AVAILABILITY STATEMENTApproved for public release, distribution is unlimited SUPPLEMENTARY NOTES 01914. ABSTRACT -Present and anticipated variation in jet propulsion fuels due to advanced engine compression ratios and airframe cooling requirements necessitate greater understanding of chemical phenomena associated with the feed system and combustion aspects of the airbreathing propulsion systems under consideration by the U.S. Air Force. With AFOSR support an integrated, fundamental research program had been established at Princeton. The focus during the subject period was directed to understanding the pyrolysis and combustion of endothermic fuels under subcritical conditions and the pyrolysis of these fuels under supercritical conditions. Main consideration was given to methylcyclohexane, decalin and tetralin, which are not only endothermic fuels, but alkylcyclohydrocarbons, the naphthene components of JP fuels. The subcritical conditions in the study were 0.1 MPa (1 atm) and temperatures ranging between 900-1200 K. The supercritical conditions were between 4-9 MPa (40-90 atm) and 720-820 K. The Princeton Turbulent Flow Reactor was used for the subcrital studies and a newly designed coiled tubular reactor for the supercritical studies. Substantial experimentation and analytical evaluation revealed distinct differences between the subcritical and supercritical results. From the rate of fuel decay under the conditions described, it was determined that, although the activation energies were of the same order, the supercritical (4.5 MPa) pre-exponential factor A was two orders of magnitude greater than the subcritical (0.1 MPa) one. Further, not only were complete scission products of all these ...

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Section: A Experimental Resultsmentioning

confidence: 99%

Section: B Review and Analysis Of Experimental Resultsmentioning

confidence: 99%

Section: B Review and Analysis Of Experimental Resultsmentioning

confidence: 99%

Section: B Review and Analysis Of Experimental Resultsmentioning

confidence: 99%

See 2 more Smart Citations

Fuels Combustion Research, Supercritical Fuel Pyrolysis

Glassman¹

1998

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“…(DV* intr ) is mainly the "mechanical" effect of pressure on the rate constant. The second contribution accounts for solvation which includes the effects of pressure on diffusion (DV* diff ), the electrostatic interactions (DV* elec ), the compressibility of the fluid phase (DV* comp = bK T ) and the phase behavior (DV* p ) [77].…”

Section: General Aspectsmentioning

confidence: 99%

Thermodynamic Aspects of Supercritical Fluids Processing: Applications of Polymers and Wastes Treatment

Cansell

Rey

Beslin

1998

Rev. Inst. Fr. Pét.

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La mise en Ïuvre des fluides supercritiques est d'un intŽr•t croissant dans de nombreux domaines : pour la sŽparation (sŽparation et purification en pŽtrochimie, industrie alimentaire) et la chromatographie par fluides supercritiques (sŽparation analytique et prŽ-paratoire, dŽtermination des propriŽtŽs physicochimiques), comme milieux rŽactifs aux propriŽtŽs continžment ajustables allant du gaz au liquide (polyŽthyl•ne de faible densitŽ, Žlimination des dŽchets, recyclage des polym•res), en gŽologie et en minŽralogie (volcanologie, Žnergie gŽothermique, synth•se hydrothermique), dans la formation des particules, fibres et substrats (produits pharmaceutiques, explosifs, rev•tements), pour le sŽchage des matŽriaux (gels).Cet article prŽsente les propriŽtŽs physicochimiques exceptionnelles des fluides supercritiques en rapport avec leurs applications en ingŽnierie. Apr•s un bref rappel des concepts fondamentaux relatifs au comportement critique des fluides purs, nous dŽvelop-pons d'une mani•re plus dŽtaillŽe les propriŽtŽs physicochimiques ajustables des fluides dans le domaine supercritique. La deuxi•me partie de lÕarticle dŽcrit les applications en ingŽnierie des fluides supercritiques relatives aux rŽactions chimiques et au traitement des polym•res. Chaque prŽsentation d'application est divisŽe en deux parties : la premi•re rappelle les concepts de base et le contexte gŽnŽral ainsi que les propriŽtŽs physicochimiques, la seconde dŽveloppe les applications en ingŽnierie se rapportant au domaine concernŽ. THERMODYNAMIC ASPECTS OF SUPERCRITICAL FLUIDS PROCESSING: APPLICATIONS TO POLYMERS AND WASTES TREATMENTSupercritical fluid processes are of increasing interest for many fields: in supercritical fluid separation (petroleum-chemistry separation and purification, food industry) and supercritical fluid chromatography (analytical and preparative separation, determination of physicochemical properties); as reaction media with continuously adjustable properties from gas to liquid (lowdensity polyethylene, waste destruction, polymer recycling); in This paper presents the unusual physicochemical properties of supercritical fluids in relation to their engineering applications. After a short report of fundamental concepts of critical behavior in pure fluids, we develop in more details the tunable physicochemical properties of fluid in the supercritical domain. The second part of this paper describes the engineering applications of supercritical fluids relevant of chemical reactions and polymer processing. Each application presentation is divided in two parts: the first one recalls the basic concepts including general background, physicochemical properties and the second one develops the engineering applications relevant of the advocated domain. ASPECTOS TERMODINçMICOS DEL TRATAMIENTO DE LOS FLUIDOS SUPERCRêTICOS : APLICACIONES PARA LOS TRATAMIENTOS DE LOS POLêMEROS Y DE LOS RESIDUOSLa implementaci-n de los fluidos supercr'ticos presenta un interŽs cada vez mayor en numerosos campos : para la separaci-n (separaci-n y purific...

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Stoichiometric Organic Reactions

Ikushima

Arai

1999

Chemical Synthesis Using Supercritical Fluids

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Solvent effects on reactions in supercritical fluids

Cited by 72 publications

References 42 publications

Fuels Combustion Research, Supercritical Fuel Pyrolysis

Fuels Combustion Research, Supercritical Fuel Pyrolysis

Thermodynamic Aspects of Supercritical Fluids Processing: Applications of Polymers and Wastes Treatment

Stoichiometric Organic Reactions

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