Relevant bibliographies by topics / Solvolisi

Academic literature on the topic 'Solvolisi'

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Published: 11 March 2023

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Journal articles on the topic "Solvolisi"

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Kevill, Dennis N., Jong Chul Kim, and Jin Burm Kyong. "Correlation of the Rates of Solvolysis of Methyl Chloroformate with Solvent Properties." Journal of Chemical Research 23, no. 2 (February 1999): 150–51. http://dx.doi.org/10.1177/174751989902300242.

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The specific rates of solvolyis of methyl chloroformate are very well correlated by the extended Grunwald–Winstein equation over a wide range of solvents; the pathway is believed to be predominantly addition–elimination, except that a positive deviation for solvolysis in 90% 1,1,1,3,3,3-hexafluoropropan-2-ol suggests an 80% contribution from an ionisation mechanism.
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Kašpárek, František, Kamila Vavčíková, Jiří Mollin, and Aleš Husek. "Steric effects in alkaline solvolysis of diaryl anilidophosphates." Collection of Czechoslovak Chemical Communications 55, no. 7 (1990): 1769–76. http://dx.doi.org/10.1135/cccc19901769.

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Analysis of the products of solvolysis of aryl esters of anilidophosphoric acids in water-2-propanol mixture excludes that the reaction proceeds via E1cB mechanism. Analysis of the reaction products of solvolysis of methyl-substituted compounds made it possible to evaluate the importance of the reported steric hindrance by CH3 group. The dependence of rate constants of the solvolysis on solvent system has been established.
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D'Souza, Malcolm J., Anthony M. Darrington, and Dennis N. Kevill. "On the Importance of the Aromatic Ring Parameter in Studies of the Solvolyses of Cinnamyl and Cinnamoyl Halides." Organic Chemistry International 2010 (June 29, 2010): 1–9. http://dx.doi.org/10.1155/2010/130506.

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In solvolysis studies using Grunwald-Winstein plots, dispersions were observed for substrates with aromatic rings at the α-carbon. Several examples for the unimolecular solvolysis of monoaryl benzylic derivatives and related diaryl- or naphthyl-substituted derivatives have now been reported, where the application of the aromatic ring parameter (I) removes this dispersion. A recent claim suggesting the presence of an appreciable nucleophilic component to the I scale has now been shown, in a review of the solvolysis of highly-hindered alkyl halides, to be unlikely to be correct. Attention is now focused on the application of the hI term for the solvolysis of compounds containing a double bond in the vicinity of any developing carbocation. Available specific rates of solvolysis (plus some new values) at 25°C of cinnamyl chloride, cinnamyl bromide, cinnamoyl chloride, p-chlorocinnamoyl chloride, and p-nitrocinnamoyl chloride are analyzed using the simple and extended (including the hI term) Grunwald-Winstein equations.
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Kumaniaev, Ivan, Elena Subbotina, Maxim V. Galkin, Pemikar Srifa, Susanna Monti, Isara Mongkolpichayarak, Duangamol Nuntasri Tungasmita, and Joseph S. M. Samec. "A combination of experimental and computational methods to study the reactions during a Lignin-First approach." Pure and Applied Chemistry 92, no. 4 (April 28, 2020): 631–39. http://dx.doi.org/10.1515/pac-2019-1002.

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AbstractCurrent pulping technologies only valorize the cellulosic fiber giving total yields from biomass below 50 %. Catalytic fractionation enables valorization of both cellulose, lignin, and, optionally, also the hemicellulose. The process consists of two operations occurring in one pot: (1) solvolysis to separate lignin and hemicellulose from cellulose, and (2) transition metal catalyzed reactions to depolymerize lignin and to stabilized monophenolic products. In this article, new insights into the roles of the solvolysis step as well as the operation of the transition metal catalyst are given. By separating the solvolysis and transition metal catalyzed hydrogen transfer reactions in space and time by applying a flow-through set-up, we have been able to study the solvolysis and transition metal catalyzed reactions separately. Interestingly, the solvolysis generates a high amount of monophenolic compounds by pealing off the end groups from the lignin polymer and the main role of the transition metal catalyst is to stabilize these monomers by transfer hydrogenation/hydrogenolysis reactions. The experimental data from the transition metal catalyzed transfer hydrogenation/hydrogenolysis reactions was supported by molecular dynamics simulations using ReaXFF.
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Park, Kyoung Ho, Mi Hye Seong, Jin Burm Kyong, and Dennis N. Kevill. "Rate and Product Studies with 1-Adamantyl Chlorothioformate under Solvolytic Conditions." International Journal of Molecular Sciences 22, no. 14 (July 9, 2021): 7394. http://dx.doi.org/10.3390/ijms22147394.

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A study was carried out on the solvolysis of 1-adamantyl chlorothioformate (1-AdSCOCl, 1) in hydroxylic solvents. The rate constants of the solvolysis of 1 were well correlated using the Grunwald–Winstein equation in all of the 20 solvents (R = 0.985). The solvolyses of 1 were analyzed as the following two competing reactions: the solvolysis ionization pathway through the intermediate (1-AdSCO)+ (carboxylium ion) stabilized by the loss of chloride ions due to nucleophilic solvation and the solvolysis–decomposition pathway through the intermediate 1-Ad+Cl− ion pairs (carbocation) with the loss of carbonyl sulfide. In addition, the rate constants (kexp) for the solvolysis of 1 were separated into k1-Ad+Cl− and k1-AdSCO+Cl− through a product study and applied to the Grunwald–Winstein equation to obtain the sensitivity (m-value) to change in solvent ionizing power. For binary hydroxylic solvents, the selectivities (S) for the formation of solvolysis products were very similar to those of the 1-adamantyl derivatives discussed previously. The kinetic solvent isotope effects (KSIEs), salt effects and activation parameters for the solvolyses of 1 were also determined. These observations are compared with those previously reported for the solvolyses of 1-adamantyl chloroformate (1-AdOCOCl, 2). The reasons for change in reaction channels are discussed in terms of the gas-phase stabilities of acylium ions calculated using Gaussian 03.
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Pytela, Oldřich, Stanislava Štumrová, Miroslav Ludwig, and Miroslav Večeřa. "Kinetic acidity function and solvolysis of 3-hydroxy-1,3-diphenyltriazenes." Collection of Czechoslovak Chemical Communications 51, no. 3 (1986): 564–72. http://dx.doi.org/10.1135/cccc19860564.

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Ten 3-hydroxy-1-(X-phenyl)-3-phenyltriazines have been synthesized, and kinetics of their solvolysis have been measured in 40% (v/v) ethanol and sulphuric acid. The concept of kinetic acidity function has been generalized, its construction has been suggested, and the procedure has been applied to the solvolysis of 3-hydroxy-1,3-diphenyltriazenes. The kinetic acidity function found has been confronted with the H0 acidity function. The substituent effects have been evaluated with respect to mechanism of the acid catalyzed solvolysis.
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D’Souza, Malcolm J., Jeremy Wirick, Osama Mahmoud, Dennis N. Kevill, and Jin Burm Kyong. "The Influence of a Terminal Chlorine Substituent on the Kinetics and the Mechanism of the Solvolyses of n-Alkyl Chloroformates in Hydroxylic Solvents." International Journal of Molecular Sciences 21, no. 12 (June 19, 2020): 4387. http://dx.doi.org/10.3390/ijms21124387.

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A previous study of the effect of a 2-chloro substituent on the rates and the mechanisms of the solvolysis of ethyl chloroformate is extended to the effect of a 3-chloro substituent on the previously studied solvolysis of propyl chloroformate and to the effect of a 4-chloro substituent on the here reported rates of solvolysis of butyl chloroformate. In each comparison, the influence of the chloro substituent is shown to be nicely consistent with the proposal, largely based on the application of the extended Grunwald–Winstein equation, of an addition-elimination mechanism for solvolysis in the solvents of only modest solvent ionizing power, which changes over to an ionization mechanism for solvents of relatively high ionizing power and low nucleophilicity, such as aqueous fluoroalcohols with an appreciable fluoroalcohol content.
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D’Souza, Malcolm J., Zoon Ha Ryu, Byoung-Chun Park, and Dennis N. Kevill. "Correlation of the rates of solvolysis of acetyl chloride and α-substituted derivatives." Canadian Journal of Chemistry 86, no. 5 (May 1, 2008): 359–67. http://dx.doi.org/10.1139/v08-028.

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Additional specific rates of solvolysis have been determined for acetyl chloride and diphenylacetyl chloride. These are combined with literature values to carry out correlation analyses, using the extended Grunwald–Winstein equation with incorporation of literature values for solvent nucleophilicity (NT) and solvent ionizing power (YCl). Parallel analysis are carried out using literature values for the specific rates of solvolysis of trimethylacetyl chloride, chloroacetyl chloride, phenylacetyl chloride, and α-methoxy-α-trifluoromethylphenylacetyl chloride (MTPAC). Chloroacetyl chloride and MTPAC react by an addition-elimination pathway, with the addition step rate-determining, over the full range of solvents. Acetyl chloride reacts over the full range of solvents by an ionization pathway, with considerable nucleophilic solvation. The other three substrates can solvolyze with the domination of either mechanism, depending on the properties of the solvent. Reports concerning the use of product selectivity values, kinetic solvent isotope effects, and computational studies as additional probes of the mechanism of solvolysis are discussed.Key words: Grunwald-Winstein equation, acyl chlorides, mechanism of solvolysis, solvent nucleophilicity.
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Conner, John K., Johanna Haider, MN Stuart Hill, Howard Maskill, and Monique Pestman. "The mechanism of solvolysis of 2-adamantyl azoxytosylate: isotopic labelling, medium effect, and attempted deoxygenation studies." Canadian Journal of Chemistry 76, no. 6 (June 1, 1998): 862–68. http://dx.doi.org/10.1139/v98-071.

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Rates of solvolysis of 2-adamantyl azoxytosylate (1) have been measured over a range of temperatures in ethanoic acid, methanoic acid, 50:50 (v/v) trifluoroethanol:water, 80:20 (v/v) trifluoroethanol:water, 97:3 (w/w) trifluoroethanol:water, and 70:30 (v/v) ethanol:water. For comparison, rates of solvolysis of 2-adamantyl tosylate (2) have also been measured in 50:50, 80:20, and 90:10 (v/v) trifluoroethanol:water, and for both compounds, activation parameters have been determined. These and results published earlier allow a correlation of the two reactions and indicate that the m value for 2-adamantyl azoxytosylate solvolysis is only 0.46. This is one of the lowest m values for a reaction that is unambiguously an SN1 solvolysis. We have also recorded the 17O NMR spectrum of the 2-adamantyl tosylate formed from 17O-labelled 2-adamantyl azoxytosylate in deuteriochloroform, and the millimeter-wave spectrum of the nitrous oxide evolved in the hydrolysis of 18O-labelled 2-adamantyl azoxytosylate. These labelling studies have provided more detailed knowledge of the SN1 fragmentation mechanism of 1 and exclude a mechanism of reaction via rearrangement to N-nitroso,N-(2-adamantyl),O-(p-toluenesulfonyl)hydroxylamine (5). Attempted deoxygenation of 1 to give 2-adamantyl diazotosylate (8) and a subsequent fragmentation proved unsuccessful.Key words: nitrous oxide, carbenium ion, isotopic labelling, solvolysis, m value.
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Omura, Kanji. "Solvolysis of 4-Halogeno-4-Alkyl-2,6-di-tert-butylcyclohexa-2,5-dienones Induced by Positive Halogen Donors as Electrophiles." Australian Journal of Chemistry 66, no. 11 (2013): 1386. http://dx.doi.org/10.1071/ch13257.

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Positive halogen donors such as N-iodosuccinimide (NIS) induce solvolysis of dienones 1, as model 4-halogenocyclohexa-2,5-dienones, in different hydroxylic solvents (ROH), yielding the 4-RO-cyclohexa-2,5-dienones (2). The rate of the solvolysis with NIS is highly dependent on the structure of ROH. The problem of such dependency is overcome by running the reaction in ROH diluted with MeCN, a polar aprotic solvent, in place of pure ROH; the rate of the reaction in the ROH-MeCN solvent mixture is almost independent of the structure (or the polarity) of ROH, and the reaction is completed faster or markedly faster than in neat ROH. The results suggest that the solvolysis rate is controlled by the polarity of the solvent system, although the hydrogen-bond acceptability of MeCN for dilution also accelerates the reaction. A mechanism for the solvolysis is proposed, involving electrophilic attack of a positive halogen donor at the halogen atom of 1, generating the 4-oxocyclohexa-2,5-dienyl cation intermediates (8) via the rate-limiting polar transition states.
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Dissertations / Theses on the topic "Solvolisi"

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Bolognesi, Simona. "Studio di un processo di riciclo di materiali polistirenici mediante solvolisi." Master's thesis, Alma Mater Studiorum - Università di Bologna, 2018. http://amslaurea.unibo.it/16218/.

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The aim of this work is to investigate a solvolysis process for recycling polystirenic materials either expanded and not, with the target to identify the main design conditions for an industrial plant which provides for successive cycles of dissolution and precipitation to separate the polymer from the flame retardant agent: hexabromocyclododecane (HBCD). In fact the current legislation allows the use of recycled GPPS (General Purpose PolyStyrene) only with a concentration of HBCD less than 100 ppm, because this agent is persistent, bioaccumulative and toxic. The experimental work has been developed through several phases. In the first phase a laboratory set-up was implemented to study the solubilization process of the polymer with dialkylcarbonates or their mixtures and the subsequent precipitation with butanol. In this context, various agitation systems and feeding methods of the mixtures have been experimented to evaluate the influence of fluid dynamics on the process. The following phases were focused on the identification and experimental validation of other solvent / non-solvent couples, keeping the toxicity for humans and the environment as a mandatory parameter. A helpful tool in the search for more efficient solvent / non-solvent pairs in purifying the polymer from HBCD (requiring less cycles of dissolution and subsequent precipitation) was found in HSPiP software, based on Hansen's solubility parameters and allowing to overcome the lack of data in the literature. Then, the experimental set up was implemented and the operating conditions were optimized to obtain the best precipitate and selected the most efficient solvent / non-solvent couple in removing HBCD.
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2

Henry, Lucile. "Étude et développement d'un procédé propre et innovant de traitement de la surface de fibres céramiques en conditions hydrothermales." Thesis, Bordeaux, 2016. http://www.theses.fr/2016BORD0328.

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Cette thèse s’inscrit dans une volonté d’adapter un procédé hydrothermal au traitement de la surface de fibres céramiques utilisées lors de la fabrication des composites à matrice céramique (CMCs). Le procédé conventionnel développé par la société Safran Ceramics se réalise en plusieurs étapes dont la principale consiste à dissoudre les phases oxydées de la surface des fibres Nicalon dans des bains d’acides. En conséquence, leurs propriétés chimiques de surface sont homogènes et un film de carbone microporeux est généré à la surface des fibres afin d’améliorer sa compatibilité chimique avec l’interphase de pyrocarbone qui y est déposée. Nous avons proposé de substituer ce procédé par un traitement par voie hydrothermale. En effet, l’eau possédant des propriétés physicochimiques ajustables en fonction des paramètres pression et température, il a été possible de modifier les propriétés de surface des fibres Nicalon d’une manière identique être productible au procédé conventionnel. L’efficacité et la compétitivité de ce traitement ont pu être démontrées par l’obtention de fibres avec des propriétés de surface optimales en une seule étape. Par la suite, l’étude du mécanisme réactionnel a révélé une attaque sélective des atomes de Si de la fibre selon des réactions d’hydrolyse. Puis, l’étude thermodynamique réalisée a mis en avant un régime à dominante cinétique. Finalement, les propriétés mécaniques des composites fabriqués à partir de tissus de fibres traités selon ce nouveau procédé ont été conformes aux objectifs. Ceci nous a donc permis de qualifier le traitement des fibres Nicalon par voie hydrothermale
This thesis project was carried out in order to develop a hydrothermal processfor the surface treatment of ceramic fibres which are integrated into the fabrication of ceramicmatrix composites (CMCs). A conventional process was developed by Safran Ceramics tomodify the surface chemistry of the Nicalon fibres following 3 steps. The main step consistsin dissolving the oxidised phases at the fibre surface by the use of strong acids. As aconsequence, the chemical homogeneity of the surface is enhanced and a microporouscarbon film is generated helping its compatibilization with the pyrocarbon interphase that isdeposited in between the fibres and the matrix. It was suggested to substitute thisconventional process by a hydrothermal treatment. Indeed, as water displays tunablephysico-chemical properties regarding the temperature and pressure conditions, it waspossible to recover fibres demonstrating reproducible and similar characteristics. Theefficiency and competitivity of the hydrothermal treatment have been assessed throughoptimised surface properties obtained after one single step. Next, the mechanisminvestigation revealed a selective attack of the Si atoms contained in the fibre via hydrolysisreactions. Then, the thermodynamic study pointed out the fact that the process wasdominated by a kinetic regim. Finally, the mechanical caracterisation of the CMCs made ofhydrothermal treated fibres showed results which met all the requirements. These finalobservations allowed us to complete the qualification of the hydrothermal process to treat thesurface of Nicalon fibres
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Khiari, Karim. "Contribution à l'étude des propriétés thermo-physiques des biocarburants de seconde génération et leur influence sur le comportement des moteurs." Thesis, Nantes, Ecole des Mines, 2016. http://www.theses.fr/2016EMNA0314/document.

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La croissance mondiale, économique et industrielle, ainsi que la rapide progression démographique des populations, ont fait augmenter la demande en énergie fossile. Ces dernières années, beaucoup de recherches ont été orientées vers de nouvelles ressources énergétiques qui peuvent remplacer les carburants fossiles conventionnels. Les biocarburants sont des carburants écologiques renouvelables, obtenus grâce à la transformation des matières grasses animales et végétales. Ils sont classés en tant que ressource idéale, non-toxique et renouvelable, substituant avantageusement le Diesel conventionnel. Dans cette optique, nous nous sommes intéressés à la production des biocarburants à partir d’une source végétale, non alimentaire, très abondante dans le bassin méditerranéen, en l’occurrence le pistachier lentisque, par deux procédés, l’un est chimique appelé transestérification et l’autre est thermochimique, la solvolyse. Les caractérisations des biocarburants conformément aux normes en vigueur, ont montré que les propriétés physico-chimiques sont comparables à celles du Diesel conventionnel. Un moteur Diesel monocylindre refroidi à l'air, a été utilisé pour évaluer les caractéristiques de la combustion de ces biocarburants, à 1500 tr/min, sous diverses conditions de charges du moteur. Les caractéristiques de la combustion (pression du cylindre, délai d’auto-inflammation, taux de dégagement de chaleur et durée de combustion) des biocarburants obtenus, sont comparées à celles du Diesel conventionnel
The world economic and industrial growths, as well as the demographic rapid progression, have increased the fossil energy demand. These last years, much of researches were directed towards new energy resources which can replace the conventional fossil fuels. The biofuels are renewable ecological fuels derived from biomass; they are classified as an ideal resource, non-toxic and renewable component with respect to the conventional Diesel. In this context, we were firstly interested to the production of the biofuels starting from a non-edible vegetable source widely available in the Mediterranean basin which is the Pistacia Lentiscus using two processes. The first one is a chemical method named “transesterification” and the second one is a thermochemical procedure called “solvolysis”. The biofuels physicochemical properties, measured via standard methods, are similar to those of Diesel fuel. A single cylinder, naturally aspirated DI Diesel engine is operated at 1500 rpm with either pure produced biofuels or their blends with Diesel fuel for several ratios (50, 30 and 5 v%) and engine load conditions. The combustion parameters, their blends are compared with those of Diesel fuel
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4

Chaabani, Chayma. "Composites à fibres de carbone : récupération des fibres par solvolyse hydrothermale. Impact sur la qualité des fibres et valorisation de la phase liquide." Thesis, Ecole nationale des Mines d'Albi-Carmaux, 2017. http://www.theses.fr/2017EMAC0011/document.

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La demande mondiale des composites à fibres de carbone est en forte croissance. Les résidus qui en découlent augmentent également. Le procédé de solvolyse a été étudié pour recycler les fibres de carbone et valoriser la résine décomposée dans la phase liquide. L’étude se focalise sur l’impact du procédé batch (température et temps de réaction) sur la disparition de la résine dans l’eau sous- et supercritique. Le procédé batch n’est pas limité par la pénétration de l’eau dans un lit de composite, mais par contre, la haute teneur en composés organiques semble initier un phénomène de repolymérisation. Aux conditions optimales (350°C, 30 min et 400°C, 15 min) les fibres sont dépourvues de résine PA6, et les propriétés mécaniques sont proches des fibres vierges. Les analyses de diffraction des rayons X montrent une modification des distances inter-réticulaires des empilements de graphène, et la spectroscopie Raman met en évidence des modifications de la structure turbostratique des fibres. Ainsi le procédé de solvolyse a conduit à des changements nanostructuraux. Les valeurs de résistance à la traction sont assez proches de celles des fibres vierges. Ainsi, les fibres peuvent être réutilisées dans la reformulation de nouveaux composites. Enfin, l’étude cinétique basée sur les valeurs d’énergie d’activation en eau sous-critique (77,79 kJ/mol) et en eau supercritique (78,51 kJ/mol) montre qu’il s’agit du même schéma mécanistique régissant la réaction de dépolymérisation de la résine. La composition de la phase liquide montre la récupération de 70 % de monomère caprolactame et de la formation de produits plus lourds dans les temps de réaction relativement long (>45min). Ceci a été expliqué par un phénomène de repolymérisation. L’utilisation du CeO2 a permis d’une part de limiter des réactions indésirables et d’autres part d’améliorer la conversion de la résine PA6 en son monomère dans les temps de réaction courts
The global demand of carbon fibers reinforced composites increases greatly, resulting in an increase of its residues. The solvolysis process has been studied in the framework of the recycling of carbon fibers and the recovery of the resin decomposed in the liquid phase. First, the study focuses on the impact of the batch process (temperature and reaction time) on the resin removal under subcritical and supercritical water. Although the batch process is not limited by the water diffusion into the composite bed, a large amount of organics results in a repolymerization phenomenon. The optimal conditions (350 °C, 30 min and 400 °C, 15 min) led to achieve the PA6 resin removal and the mechanical properties of recovered carbon fibers are similar to the virgin ones. The X-ray diffraction patterns show a modification of the inter-reticular distances of the graphene stacks, and Raman spectroscopy analysis reveal a modification in the turbostratic structure. Therefore nanostructural changes have occurred due to solvolysis process. Tensile strength values are quite similar to those of the virgin fibers, thus the fibers can be reused in the reformulation of new composites. Finally, the kinetic study based on the values of activation energy in subcritical water (77.79 kJ / mol) and in supercritical water (78.51 kJ / mol) shows that the same mechanistic scheme is governing the resin depolymerization reaction. The composition of the liquid phase shows the recovery of 70 % the monomer (caprolactam) and the production of heavier products in long reaction times (>45min). This has been explained by a repolymerization phenomenon. The use of CeO2 was efficient to limit undesirable reactions and to improve the conversion of the PA6 resin into its monomer in short reaction times
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Ould, Amara Salem. "Matériaux à base de bore pour des applications énergies." Thesis, Montpellier, 2017. http://www.theses.fr/2017MONTT180/document.

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Cette thèse s’articule autour de matériaux à base de bore pour des applications « énergie ». Nous avons développé deux classes de matériaux. (i) La première classe est dédiée au stockage chimique de l’hydrogène. Les matériaux étudiés dans cette partie sont produits par déstabilisation par mécanosynthèse de l’hydrazine borane N2H4BH3 en substituant un hydrogène protique de ce dernier par un cation alcalin. Nous avons particulièrement étudié la modification chimique de l’hydrazine borane par l’amidure de lithium LiNH2, puis par l’hydrure du calcium CaH2. Dans le premier cas, un nouveau composé de formule LiN2H3BH3.0,25NH3 a été obtenu. Dans le second cas, l’hydrazinidoborane de calcium Ca(N2H3BH3)2 a été synthétisé dans des conditions expérimentales spécifiques. (ii) La deuxième classe de matériaux concerne les polyboranes anioniques solubles dans l’eau pour une utilisation comme combustible anodique de pile à combustible liquide. Nous avons synthétisé et pleinement caractérisé le closo-décaborane de sodium Na2B10H10 et le 1-oxa-nido-dodécaborate de sodium NaB11H12O, puis leur électrooxydation a été étudiée et discutée sur différentes électrodes massives (platine, or et argent). Tous nos résultats sont présentés, discutés en détail et mis en perspective dans ce manuscrit de thèse
The present work is structured around boron-based materials expected to be used in the field of “energy”. We especially worked on two types of materials. (i) With the first type, solid-state hydrogen storage was targeted. Hydrazine borane N2H4BH3 was used as precursor of novel derivatives obtained by mechanosynthesis. We first made it react with lithium amide LiNH2 to obtain LiN2H3BH3.0,25NH3. Then, we considered calcium hydride CaH2; it reacted with N2H4BH3 at 67°C (after ball-milling) to form a new phase, calcium hydrazinidoborane of formula Ca(N2H3BH3)2. (ii) The second type of boron-based materials we investigated is about anionic polyboranes. They are known to be stable in aqueous solution and accordingly could be used as anodic fuel of direct liquid-fed fuel cell. We aimed at synthesizing and fully characterizing two salts: sodium closo-decaborane Na2B10H10 and sodium 1-oxa-nido-dodecaborate NaB11H12O. Their potential for the aforementioned application was tested by cyclic voltammetry by using bulk electrodes of platinum, silver and gold. All of our results are presented, discussed in detail and put into perspective in the present thesis
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Sebhat, Woldemichael. "Valorisation de la lignine par catalyse hétérogène en condition sous-critique en milieux aqueux et eau/alcool." Thesis, Lyon 1, 2015. http://www.theses.fr/2015LYO10273/document.

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La lignine est une macromolécule, constituant de la biomasse lignocellulosique, qui est composée d’unités propylphénoliques. Cette matière est produite par l’industrie papetière en tant que coproduit de la cellulose. Actuellement, sa valorisation se limite en grande partie à des applications énergétiques. Or, la lignine peut être une source alternative de phénols si elle est dépolymérisée efficacement. Ce travail porte sur la transformation de la lignine en synthons aromatiques dans l’eau et en mélange eau-alcools en conditions sous-critique (225°C et 40-80 bar). Dans un premier temps, des études de conversion sont réalisées en réacteur fermé en utilisant l’eau comme solvant sur une lignine Kraft en présence de catalyseurs (Pt, Pd, Ru sur Al2O3,TiO2, ZrO2), le catalyseur Pd/ZrO2 nous a permis d’obtenir un rendement en phénols identifiés de 2%en 3 heures. Afin d’améliorer la conversion de la lignine en minimisant les réactions de condensations entre unités phénoliques, l’eau est remplacée par un mélange eau/alcool (éthanol, méthanol, isopropanol). La combinaison eau/isopropanol sans catalyseur nous permet d’augmenter le rendement en phénols identifiés de 5%. Nous avons ensuite essayé d’appliquer notre approche en réacteur continu. Même si le mélange eau/isopropanol était le meilleur solvant en réacteur fermé, le passage en réacteur continu s’est avéré complexe par la formation de produits solides. L’utilisation d’un mélange eau/éthanol a permis d’éviter ce problème et un rendement en gaiacol jusqu’à 1% est obtenu. L’éthanol permet de stabiliser des synthons instables dans le milieu par alkylation et estérification
Lignin is a macromolecule comprising lignocellulosic biomass, and is composed of propylphenyl units. Lignin is produced in large amounts by the paper industry when cellulose is isolated from biomass. Currently, its value is largely limited to source of energy and heat in recovery boilers. Nonetheless lignin can be an alternative source of aromatics if depolymerized effectively. The present work focuses on the transformation of lignin into aromatic building blocks using sub-critical water and mixtures of water/alcohols (225°C and 40-80 bar). Preliminary studies were carried out in a batch reactor; water was used as a solvent for the conversion of a Kraft lignin in the presence of catalysts (Pt, Pd, Ru on Al2O3, TiO2, ZrO2). The Pd/ZrO2 catalyst gave the highest yield of identified phenols with 2% in 3 hours. To improve the conversion of the lignin by minimizing condensation reactions between phenolic units, the water was replaced with a mixture water/alcohol (ethanol, methanol, isopropanol). The combination water/isopropanol without catalyst allowed us to increase the yield of identified phenols to 5%. The results obtained in batch reactor were extrapolated to a trickle-bed reactor. Even though the water/isopropanol mixture gave the best results in batch reactor, the implementation on a continuous reactor proved to be complex (formation of solids clogging the reactor). The use of a water/ethanol mixture prevented this problem and a yield in guaiacol of up to 1 % was obtained. Ethanol helps stabilize unstable building blocks by alkylation and esterification. This is evidenced by the NMR and chromatographic analysis
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Martinelli, Andrea. "Studio di reazioni ed approcci sintetici innovativi per la sintesi di intermedi di interesse industriale." Doctoral thesis, Università degli studi di Trieste, 2014. http://hdl.handle.net/10077/10128.

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2012/2013
In questo lavoro di tesi sono state affrontati due temi principali: la risoluzione di diastereoisomeri intermedi nella sintesi della Dorzolamide e lo studio su reazioni di addizione di Michael stereoselettive su substrati chetonici a,b-insaturi con nucleofili allo zolfo. Il primo progetto si è focalizzato sull'impiego di una risoluzione cinetica dinamica per convertire due alcoli diastereomerici in un unico prodotto acilato tramite la combinazione di una reazione di acilazione promossa da enzimi (CALB e subtilisina) ed un catalizzatore di Ru in grado di epimerizzare tra loro gli alcoli. Ulteriori studi hanno permesso di indagare maggiormente su reazioni di solvolisi sui medesimi substrati che hanno permesso di ottenere il prodotto desiderato in ottima resa chimica ed eccesso enantiomerico. Il secondo progretto si è focalizzato sull'impiego di alcuni alcaloidi della Cinchona e su corrispondenti derivati tioureidici in reazioni di Michael stereoselettive. I substrati impiegati sono stati il trans-calcone ed il 2-cicloesen-1-one; nucleofili allo solfo sono stati il benziltiolo ed il tiofenolo. I tisultati ottenuti hanno permesso di verificare l'efficacia dei catalizzatori tioureidici sulle reazioni modello studiate.
XXVI Ciclo
1984
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8

Lima, Carmen de. "Solvolise de tosilatos de 1-aril-2,2,2-trialogenoetila." reponame:Repositório Institucional da UFSC, 1988. http://repositorio.ufsc.br/xmlui/handle/123456789/75464.

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Dissertação (mestrado) - Universidade Federal de Santa Catarina. Centro de Ciencias Fisicas e Matematicas
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A solvólise dos tosilatos de 2,2,2-tricloro-1-(4-metoxifenil)etanol, 2,2,2-tricloro-1-(4-metoxifenil)etanol, 2,2,2-tricloro-1-(4-metilfenil)etanol e 2,2,2-tricloro-1-(fenil)etanol foi estudada a diversas temperaturas em vários solventes polares (etanol-água, metanol-água, metanol, etanol, trifluoroetanol, ácido fórmico e ácido acético). Os dados cinéticos indicam que os tosilatos triclorados se solvolisam por um mecanismo essencialmente kc, embora com alguma possível assistência do solvente. No caso dos tosilatos tribromados, cuja solvólise é mais fácil que para os análogos triclorados, propõe-se um mecanismo solvolítico com a assistência dos átomos de bromo.
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9

Schaller, Heike. "Changes in Solvolysis Mechanisms." Diss., lmu, 2008. http://nbn-resolving.de/urn:nbn:de:bvb:19-91684.

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10

Wilhelm, Catherine. "Solvolyse de charbons et de leurs macéraux." Metz, 1990. http://docnum.univ-lorraine.fr/public/UPV-M/Theses/1990/Wilhem_Lacordaire.Catherine.SMZ9015.pdf.

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La solvolyse des charbons présente un intérêt fondamental sur le plan de la connaissance de leur structure, en vue de leurs utilisations ultérieures : carbonisation, liquefaction et gazéification. Notre objectif a été la mise au point de procédés de solvolyse et la caractérisation des produits de solvolyse, obtenus à partir d'échantillons de charbons et de leurs macéraux. L'extraction à la n-méthyl 2 pyrrolidinone (NMP) dans le cadre de la solvolyse physique et la solubilisation par le mélange méthanol/soude (MeOH/NaOH) pour la solvolyse chimique ont été réalisées parallèlement afin d'étudier la structure moléculaire du charbon. Nous avons considéré, pour cette étude, le charbon sous son modèle actuel de structure biphasique avec une composante moléculaire M s'apparentant à la phase extractible (extrait NMP) et une matrice macromoléculaire MM (résidu d'extraction) qui ne peut être étudiée que par solvolyse chimique. La comparaison des résultats de l'extraction et ceux de la caractérisation des charbons, des macéraux et des produits d'extraction, par des méthodes globales (IR/TF, RMN 13C, RPE), nous a conduit à adopter la notion de structure moléculaire plutôt que celle de macéraux pour expliquer le comportement des charbons vis-à-vis de la solvolyse. Une caractérisation complémentaire par des méthodes thermiques couplées à la spectrométrie de masse (TD-GC/MS, Py-FIMS) des produits de solvolyse nous a amené à suggérer la possibilité qu'une partie de la phase M, est non extractible est reste liée à la phase macromoléculaire MM. De ce fait, le modèle de structure biphasique représente une simplification du problème. Enfin, nous avons étudié l'influence des phases moléculaire M et macromoléculaire MM sur les proprietés optiques des cokes issus de la carbonisation des charbons et de leurs produits d'extraction. Nous avons mis évidence par microscopie électronique par transmission MET le rôle essentiel de la composition déterminée par des méthodes de fractionnement primaire (sonication US et extrographie EX) de la phase extractible à la NMP sur le comportement thermique des charbons
The solvolysis of coals represent an important way to access to coal structure, in relation to his utilization in carbonization, liquefaction or gazeification. The aim of our work was locussed on coal solvolysis and characterization of the solvolysis products obtained from coals and macerals. The N-methyl 2 Pyrrolidinone (NMP) extraction, which is a physical process of solvolysis and the solubilization by the mixture methanol/sodium hydroxide (MeOH/NaOH) were realized to study the molecular structure of coal. Coal was considered in the frame of this study, as a three-dimensional crosslinked network or "macromolecular phase" (MM), which trapped free molecules that are not covalenty bonded to the network and constituated the molecular phase (M). The comparison of the results of the extraction and the characterization of coals, macerals and extracted products by spectroscopic methods (FT/IR, Solid state 13C NMR and EPR) allowed us to consider the notion of molecular structure rather than the maceral one to explain the behaviour of coals during solvolysis. A complementary analysis by thermic methods coupled to mass spectrometry (TD GC/MS, Py-FIMS) of solvolysis products permitted us to suggest that a part of the molecular phase is not extractable by solvents and stays linked to macromolecular phase. Therefore, the hypothesis of a "two-components" structure represents a simplified model. At last, the influence of the two phases "molecular M and macromolecular MM" on optical properties of cokes obtained by carbonization of coals and extracted products was studied. We have proved by the study with Transmission Electronic Microscopy TEM the important role of the composition determined by fractionation (sonication US and extrography EX) of the NMP extractible phase on the thermal behaviour of coals
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Books on the topic "Solvolisi"

1

Phanstiel, Otto. The effect of a single fluorine substituent on the [1,5] homodienyl hydrogen shift, the solvolytic ring-opening of bromocyclopropane, and the [1,3] carbon shift of 6-methylenebicyclo[3.2.0]hept-2-ene. 1988.

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(undifferentiated), William H. Brown. Studying the Kinetics of Te Solvolysis of 2 Chloro 2 Methylpropane (Medular Laboratory Program in Chemistry). Chemical Education Resources, 1993.

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Book chapters on the topic "Solvolisi"

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Xanthos, M., and S. H. Patel. "Solvolysis." In Frontiers in the Science and Technology of Polymer Recycling, 425–36. Dordrecht: Springer Netherlands, 1998. http://dx.doi.org/10.1007/978-94-017-1626-0_20.

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Blandamer, Michael J., John M. W. Scott, and Ross E. Robertson. "Solvolysis Revisited." In Progress in Physical Organic Chemistry, 149–96. Hoboken, NJ, USA: John Wiley & Sons, Inc., 2007. http://dx.doi.org/10.1002/9780470171943.ch3.

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Robertson, R. E. "Solvolysis in Water." In Progress in Physical Organic Chemistry, 213–80. Hoboken, NJ, USA: John Wiley & Sons, Inc., 2007. http://dx.doi.org/10.1002/9780470171837.ch5.

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Elamin, A., S. Rezzoug, R. Capart, and M. Gelus. "Solvolysis and Catalytic Hydrotreatment of Wood." In Advances in Thermochemical Biomass Conversion, 1415–23. Dordrecht: Springer Netherlands, 1993. http://dx.doi.org/10.1007/978-94-011-1336-6_111.

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Bouvier, J. M., M. Gelus, and S. Maugendre. "Direct Liquefaction of Wood by Solvolysis." In ACS Symposium Series, 129–38. Washington, DC: American Chemical Society, 1988. http://dx.doi.org/10.1021/bk-1988-0376.ch013.

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Hirose, Shigeo, Shoichiro Yano, Tatsuko Hatakeyama, and Hyoe Hatakeyama. "Heat-Resistant Polyurethanes from Solvolysis Lignin." In ACS Symposium Series, 382–89. Washington, DC: American Chemical Society, 1989. http://dx.doi.org/10.1021/bk-1989-0397.ch029.

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Allen, Annette D., V. M. Kanagsabapathy, and Thomas T. Tidwell. "Solvolysis of Electron-Deficient 1-Arylethyl Tosylates." In Advances in Chemistry, 315–28. Washington, DC: American Chemical Society, 1987. http://dx.doi.org/10.1021/ba-1987-0215.ch022.

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Gallego, Mar Gómez, and Miguel A. Sierra. "Level 3 - Case 35 Solvolysis of Vinyl Iodonium Salts." In Organic Reaction Mechanisms, 231–36. Berlin, Heidelberg: Springer Berlin Heidelberg, 2004. http://dx.doi.org/10.1007/978-3-642-18788-9_35.

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Gallego, Mar Gómez, and Miguel A. Sierra. "Level 3 - Case 40 Solvolysis of 8-Deltacyclyl Brosylates." In Organic Reaction Mechanisms, 269–76. Berlin, Heidelberg: Springer Berlin Heidelberg, 2004. http://dx.doi.org/10.1007/978-3-642-18788-9_40.

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Gallego, Mar Gómez, and Miguel A. Sierra. "Level 1 — Case 9 Solvolysis of Electron-Deficient Norbornyl Triflates." In Organic Reaction Mechanisms, 55–62. Berlin, Heidelberg: Springer Berlin Heidelberg, 2004. http://dx.doi.org/10.1007/978-3-642-18788-9_9.

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Conference papers on the topic "Solvolisi"

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Oliveux, Géraldine, Eric Le Gal La Salle, Jean-Luc Bailleul, Francisco Chinesta, Yvan Chastel, and Mohamed El Mansori. "Recycling By Solvolysis Thermosetting Composite Materials Of Sustainable Surface Transport." In INTERNATIONAL CONFERENCE ON ADVANCES IN MATERIALS AND PROCESSING TECHNOLOGIES (AMPT2010). AIP, 2011. http://dx.doi.org/10.1063/1.3552442.

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Sloan, I., S. Romero, S. Ford, and K. Kooduvalli. "Embodied Energy of Pyrolysis and Solvolysis Processes for Recycling Carbon Fiber Reinforced Polymer Waste." In SAMPE 2020 | Virtual Series. NA SAMPE, 2020. http://dx.doi.org/10.33599/382/s.20.0371.

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Sloan, I., S. Romero, S. Ford, and K. Kooduvalli. "Embodied Energy of Pyrolysis and Solvolysis Processes for Recycling Carbon Fiber Reinforced Polymer Waste." In SAMPE 2020 | Virtual Series. NA SAMPE, 2020. http://dx.doi.org/10.33599/s.20.0371.

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Sloan, I., S. Romero, S. Ford, and K. Kooduvalli. "Embodied Energy of Pyrolysis and Solvolysis Processes for Recycling Carbon Fiber Reinforced Polymer Waste." In SAMPE 2020 | Virtual Series. NA SAMPE, 2020. http://dx.doi.org/10.33599/nasampe/s.20.0371.

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Singh, A. K. "Kinetics of Acid Catalyzed Solvolysis of Amyl Methanoate Formate in Water-ethylene Glycol (EG) Solvent." In 2020 9th International Conference System Modeling and Advancement in Research Trends (SMART). IEEE, 2020. http://dx.doi.org/10.1109/smart50582.2020.9337122.

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Kuznetsov, Peter, Budeebazar Avid, Lyudmila Kuznetsova, Barnazan Purevsuren, Xing Fan, Zinfer Ismagilov, and Vladimir Safin. "Thermal Solvolysis of Coals Under Mild Conditions as an Alternative Way to Produce Aromatics for Carbon Materials." In 5th International Conference on Chemical Investigation and Utilization of Natural Resource (ICCIUNR-2021). Paris, France: Atlantis Press, 2021. http://dx.doi.org/10.2991/ahcps.k.211004.015.

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Singh, Anil Kr. "Kinetics Investigation of Solvent Polarity on Reaction Rate for Solvolysis of Ethyl Caprylate Ester in Binary Solvent System." In 2021 10th International Conference on System Modeling & Advancement in Research Trends (SMART). IEEE, 2021. http://dx.doi.org/10.1109/smart52563.2021.9676306.

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Pompidou, Stéphane, Marion Prinçaud, Nicolas Perry, and Dimitri Leray. "Recycling of Carbon Fiber: Identification of Bases for a Synergy Between Recyclers and Designers." In ASME 2012 11th Biennial Conference on Engineering Systems Design and Analysis. American Society of Mechanical Engineers, 2012. http://dx.doi.org/10.1115/esda2012-82106.

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In order to decrease both energy consumption and CO2 emissions, the automotive, aeronautics and aerospace industries aim at making lighter vehicles. To achieve this, composite materials provide good opportunities, ensuring high material properties and free definition of geometry. As an example, for cold applications, the use of carbon fiber/thermoset composites is ever increasing, in spite of a high fiber price. But in a global and eco-friendly approach, the major limitation for their use remains their potential recyclability. Recycling a composite means having a recycling technology available, getting a dismantle solution and an access for the product, and disposing identification plus selection possibilities to the materials. Thus, carbon fibers recovery (i.e. recycling and re-processing) would both help design engineers to balance energy efficiency and cost, and open new opportunities for developing second-life composites, dedicated to the manufacture of medium or low loaded parts (non-structural in many cases). A first section presents an overview of composite recycling possibilities. Indeed, environmentally and economically, composite incineration is not attractive (even with an energetic valorization), let-alone burying. Reuse and recycling thus remain the two most interesting options. Aeronautics offers a high potential in terms of fiber deposit. In southwest France, composites recycling will increase in terms of quantity due to dismantling platforms Tarmac (dedicated to civil aircraft applications) and P2P (for the disassembly of ballistic weapons). In addition, from a technical point of view, and even if end-of-life solutions for composites still remain under development, solvolysis (i.e. water under supercritical conditions) already offers the opportunity to recover carbon fibers. The resulting recyclate retains up to 90 percent of the fiber’s mechanical properties. A second part will explore the recycling to design issue (i.e. how recycling processes have to balance the previous aspects of the end-of-life proposal). The recycler clearly becomes a new supplier in the carbon fiber lifecycle, by revalorizing wastes with alternatives to burning. Moreover, increasing carbon fiber shelf life reduces its product life impact. Finally, promoting carbon fiber end-of-life would ensure to link aeronautics, automotive, and leisure and sports industries; but one can create demand for recycled reinforcement, by packaging it in useful and attractive forms for those end-users (e.g. pseudo-continuous fiber, felt, strips, bands, patches, etc.). These sections will be enlightened by several examples from collaborations between I2M and local industries.
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Reports on the topic "Solvolisi"

1

Braun, Andre M. Enhanced Oxidation and Solvolysis Reactions in Chemically Inert Microheterogeneous Systems. Fort Belvoir, VA: Defense Technical Information Center, January 1986. http://dx.doi.org/10.21236/ada191248.

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Braun, Andre M. Enhanced Oxidation and Solvolysis Reactions in Chemically Inert Microheterogeneous Systems. Fort Belvoir, VA: Defense Technical Information Center, August 1985. http://dx.doi.org/10.21236/ada191250.

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Braun, Andre M. Enhanced Oxidation and Solvolysis Reactions in Chemically Inert Microheterogeneous Systems. Fort Belvoir, VA: Defense Technical Information Center, January 1987. http://dx.doi.org/10.21236/ada191251.

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Braun, Andre M. Enhanced Oxidation and Solvolysis Reactions in Chemically Inert Microheterogeneous Systems. Fort Belvoir, VA: Defense Technical Information Center, October 1987. http://dx.doi.org/10.21236/ada191252.

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Eliel, Ernest L. Neighboring Group Participation in Solvolysis of Organosulfur and Related Compounds. Fort Belvoir, VA: Defense Technical Information Center, August 1985. http://dx.doi.org/10.21236/ada161458.

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