Highly Efficient and Reproducible Nonfullerene Solar Cells from Hydrocarbon Solvents

KAUST Repository

Wadsworth, Andrew

2017-06-01

With chlorinated solvents unlikely to be permitted for use in solution-processed organic solar cells in industry, there must be a focus on developing nonchlorinated solvent systems. Here we report high-efficiency devices utilizing a low-bandgap donor polymer (PffBT4T-2DT) and a nonfullerene acceptor (EH-IDTBR) from hydrocarbon solvents and without using additives. When mesitylene was used as the solvent, rather than chlorobenzene, an improved power conversion efficiency (11.1%) was achieved without the need for pre- or post-treatments. Despite altering the processing conditions to environmentally friendly solvents and room-temperature coating, grazing incident X-ray measurements confirmed that active layers processed from hydrocarbon solvents retained the robust nanomorphology obtained with hot-processed chlorinated solvents. The main advantages of hydrocarbon solvent-processed devices, besides the improved efficiencies, were the reproducibility and storage lifetime of devices. Mesitylene devices showed better reproducibility and shelf life up to 4000 h with PCE dropping by only 8% of its initial value.

Covalent biofunctionalization of silicon nitride surfaces

NARCIS (Netherlands)

Arafat, A.; Giesbers, M.; Rosso, M.; Sudhölter, E.J.R.; Schroën, C.G.P.H.; White, R.G.; Li Yang,; Linford, M.R.; Zuilhof, H.

2007-01-01

Covalently attached organic monolayers on etched silicon nitride (SixN4; x 3) surfaces were prepared by reaction of SixN4-coated wafers with neat or solutions of 1-alkenes and 1-alkynes in refluxing mesitylene. The surface modification was monitored by measurement of the static water contact angle,

Ruthenium-catalysed synthesis of 2- and 3-substituted quinolines from anilines and 1,3-diols

DEFF Research Database (Denmark)

Monrad, Rune Nygaard; Madsen, Robert

2011-01-01

A straightforward synthesis of substituted quinolines is described by cyclocondensation of anilines with 1,3-diols. The reaction proceeds in mesitylene solution with catalytic amounts of RuCl3·xH 2O, PBu3 and MgBr2·OEt2. The transformation does not require any stoichiometric additives and only...

Design of a cold neutron source for 25MeV Linac of CAB (Centro Atomico Bariloche - Argentina)

International Nuclear Information System (INIS)

Torres, Lourdes

2006-01-01

Cold neutrons are widely used in fields of research such as the dynamics of solids and liquids, the investigation of magnetic materials, material science, biology, and nuclear physics in general. Accelerator-based cold neutron sources have already proved to be well adapted to perform neutron scattering studies in all those fields.In this work we present the design of a cold neutron source in the electron Linac-based pulsed source at Centro Atomico Bariloche.The objective of this work is to develop an inexpensive yet efficient cold source with a simple moderator material.Although ideal materials for that purpose would be solid methane or liquid H2, due to economical and safety reasons light water ice, benzene or solid mesitylene were considered as cold moderators. In order to proceed with the design and optimization process of the neutron source, total cross sections for light water ice, benzene and mesitylene were measured at low temperature and thermal nuclear data libraries for such materials had to be developed.The purpose of these calculations was to optimize shape and size for the moderator at a working temperature.To calculations were performed using the MCNP-4C code and our libraries, together with files for (free-atom) carbon, hydrogen and oxygen at that temperature.The geometry studied consisted of a neutron source and different moderator (slab, cylindrical slab, grids, and sets premoderator - moderator with and without coupled).To simplify the system cooler, the slab geometry was changed to a coin shaped moderator using liquid nitrogen as cooler.From the variety of simulations performed, it was clear that a premoderator was necessary to obtain higher intensities.Furthermore, with a premoderator the thickness of the moderator was reduced, simplifying the cooling system.Finally, we adopted for our cold neutron source, a slab premoderator of PLE at room temperature, and a cylindrical moderator of mesitylene at 89K with a cooler system of stainless steel with

Temperature Dependence of the Inhibition of Positronium by Chlorine- Substituted Hydrocarbons in Non-Polar Liquids

DEFF Research Database (Denmark)

Wikander, G.; Mogensen, O.E.; Pedersen, Niels Jørgen

1984-01-01

Positron annihilation lifetime spectra were measured for solutions of 1,2,3,5-C6H2Cl4 in hexane, toluene, m-xylene and mesitylene, CCl4 in hexane and toluene, and C2HCl3 in n-hexane for concentrations below 1 M and at various temperatures between −30°C and 67°C. The Ps inhibition by C6H2Cl4 was r...

Matrix isolation study of the interaction between water and the aromatic π-electron system

International Nuclear Information System (INIS)

Engdahl, A.; Nelander, B.

1987-01-01

The interaction of water (H 2 O, D 2 O, HDO) with toluene, the xylenes, pseudocumene, mesitylene, pentamethylbenzene, and hexamethylbenzene in argon matrices has been studied with infrared spectroscopy. Interaction energy estimates are given. The shapes of the observed absorption bands suggest that water executes a complicated motion relative to the ring plane of the aromatic hydrocarbon. The infrared spectrum of the benzene-water complex has been recorded as a function of temperature in argon, krypton, and nitrogen matrices

Accelerator-based neutron source and its future

International Nuclear Information System (INIS)

Kiyanagi, Yoshiaki

2008-01-01

Neutrons are useful tool for the material science and also for the industrial applications. Now, high intensity neutron sources based on MW class big accelerators are under commissioning in Japan, Japan Spallation Neutron Source (JSNS) at J-PARC and in the US, SNS. Such high power neutron sources required the moderators that can be used under high radiation field and also give high neutronic performance. We have been performing experimental and Monte Carlo simulation studies to develop the cold neutron moderator systems for the high power sources since it is becoming important for materials and life science. Hydrogen is the unique candidate at the present stage due to its high resistibility to the radiation. It was indicated the para hydrogen moderator gave a good neutronic performance by experimental results. On the other hand, in the future, low power neutron sources are recognized to be useful to perform sprouting experiments and to promote the neutron science. The moderator systems need a concept different from the high power source. Therefore, we studied neutronic performances of the mesitylene and the methane moderators to get high intensity in a definite area on the moderator surface. Single groove moderators were studied and optimal geometry and the intensity gain were obtained. The mesitylene moderator gave a rather good performance compared to the methane moderator. (author)

Effect of temperature on photochemical smog reactions

Energy Technology Data Exchange (ETDEWEB)

Bufalini, J J; Altshuller, A P

1963-01-01

In the present investigation the photo-oxidation reactions to trans-2-butene-nitric oxide and 1,3,5-trimethylbenzene (mesitylene)-nitric oxide in air have been followed. The rates of formation and disappearance of nitrogen dioxide and the rate of reaction of the hydrocarbons have been measured at 20 and 40/sup 0/. The results obtained indicate about a twofold decrease in conversion times over the 20/sup 0/ interval and a corresponding increase in rates of reactions. 5 references.

Experimental study on a cold neutron source of solid methylbenzene

Energy Technology Data Exchange (ETDEWEB)

Utsuro, M; Sugimoto, M; Fujita, Y [Kyoto Univ., Kumatori, Osaka (Japan). Research Reactor Inst.

1975-10-01

An experimental study to produce cold neutrons with low temperature solid mesitylene as cold moderator in liquid helium and liquid nitrogen cryostats is reported. Measured cold neutron spectra by using an electron linac and time-of-flight method shows that this material is a better cold moderator than light water ice, giving the cold neutron output not so much inferior to that of solid methane in the temperature range above about 20 K and in the neutron energy region above about 1 MeV.

Chlorination of (PheboxIr(mesityl(OAc by Thionyl Chloride

Directory of Open Access Journals (Sweden)

Meng Zhou

2015-06-01

Full Text Available Pincer (PheboxIr(mesityl(OAc (2 (Phebox = 3,5-dimethylphenyl-2,6-bis(oxazolinyl complex, formed by benzylic C-H activation of mesitylene (1,3,5-trimethylbenzene using (PheboxIr(OAc2OH2 (1, was treated with thionyl chloride to rapidly form 1-(chloromethyl-3,5-dimethylbenzene in 50% yield at 23 °C. A green species was obtained at the end of reaction, which decomposed during flash column chromatography to form (PheboxIrCl2OH2 in 87% yield.

Study of Electrical Transport Properties of Thin Films Used as HTL and as Active Layer in Organic Solar Cells, through Impedance Spectroscopy Measurements

Directory of Open Access Journals (Sweden)

Camilo A. Otalora

2016-01-01

Full Text Available Impedance spectroscopy (IS is used for studying the electrical transport properties of thin films used in organic solar cells with structure ITO/HTL/active layer/cathode, where PEDOT:PSS (poly(3,4-ethylenedioxythiophene:polystyrene sulfonic acid and CuPC (tetrasulfonated copper-phthalocyanine were investigated as HTL (hole transport layer and P3HT:PCBM (poly-3-hexylthiophene:phenyl-C61-butyric acid methyl ester blends prepared from mesitylene and chlorobenzene based solutions were studied as active layer and Ag and Al were used as cathode. The study allowed determining the influence of the type of solvent used for the preparation of the active layer as well as the speed at which the solvents are removed on the carriers mobility. The effect of exposing the layer of P3HT to the air on its mobility was also studied. It was established that samples of P3HT and P3HT:PCBM prepared using mesitylene as a solvent have mobility values significantly higher than those prepared from chlorobenzene which is the solvent most frequently used. It was also determined that the mobility of carriers in P3HT films strongly decreases when this sample is exposed to air. In addition, it was found that the electrical properties of P3HT:PCBM thin films can be improved by removing the solvent slowly which is achieved by increasing the pressure inside the system of spin-coating during the film growth.

Synthesis and animal experiment of 99mTc-labeled hepatobiliary imaging agents

International Nuclear Information System (INIS)

Zhou Xirui; Chen Shaoliang; Chen Guohui; Xu Qinfeng

1993-01-01

Six new compounds based on the principle of isosterism and hybridization had been synthesized. Methobrofenin was prepared by reduction of nitro mesitylene, followed by bromination and acylation with nitrilotriacetic acid. The 99m Tc-complexes of these compounds were prepared by stannous chloride reduction of sodium pertechnetate in aqueous solution. These labeled compounds, being similar to 99m Tc-mebrofenin, all were quick in the uptake by the liver cells, rapidly cleared off from the blood in mice, and had higher cumulative hepatobiliary excretion rates than Tc-99m-EHIDA

Silver-Catalyzed Dehydrogenative Synthesis of Carboxylic Acids from Primary Alcohols

DEFF Research Database (Denmark)

Ghalehshahi, Hajar Golshadi; Madsen, Robert

2017-01-01

A simple silver-catalyzed protocol has been developed for the acceptorless dehydrogenation of primary alcohols into carboxylic acids and hydrogen gas. The procedure uses 2.5 % Ag2 CO3 and 2.5-3 equiv of KOH in refluxing mesitylene to afford the potassium carboxylate which is then converted...... into the acid with HCl. The reaction can be applied to a variety of benzylic and aliphatic primary alcohols with alkyl and ether substituents, and in some cases halide, olefin, and ester functionalities are also compatible with the reaction conditions. The dehydrogenation is believed to be catalyzed by silver...

Phosphorene quantum dots

Science.gov (United States)

Vishnoi, Pratap; Mazumder, Madhulika; Barua, Manaswee; Pati, Swapan K.; Rao, C. N. R.

2018-05-01

Phosphorene, a two-dimensional material, has been a subject of recent investigations. In the present study, we have prepared blue fluorescent phosphorene quantum dots (PQDs) by liquid phase exfoliation of black phosphorus in two non-polar solvents, toluene and mesitylene. The average particle sizes of PQDs decrease from 5.0 to 1.0 nm on increasing the sonicator power from 150 to 225 W. The photoluminescence spectrum of the PQDs is red-shifted in the 395-470 nm range on increasing the excitation-wavelength from 300 to 480 nm. Electron donor and acceptor molecules quench the photoluminescence, with the acceptors showing more marked effects.

Investigation into radiolysis of tbp labelled with 32P in the 30%tbp-diluent-HNO3 systems

International Nuclear Information System (INIS)

Novak, M.; Novak, Z.; Rokhon', A.

1975-01-01

Phosphorus-containing compounds, prepared by radiolysis of the TBP-diluent-HNO 3 system, are determined quantitatively. Effects of the HNO 3 concentration and the diluent type upon the degree of the TBP decomposition in the system under investigation were determined as well. To separate the TBP decomposition products the thin layer chromatography method was used, and for the quantitative determination TBP, labelled with 32 P was used. As a result of TBP radiolysis except dibutyl phosphate and monobutylphosphate other compounds are prepared, which contain phosphorus in a molecule, besides, their quantity depends on the nitric acid concentration and the diluent type (n-dodecan, carbon tetrachloride, mesitylen), together with which TBP was irradiated. The prepared compounds are grouped in the aqueous and organic phases

Carbon dioxide hydrogenation to aromatic hydrocarbons by using an iron/iron oxide nanocatalyst

Directory of Open Access Journals (Sweden)

Hongwang Wang

2014-06-01

Full Text Available The quest for renewable and cleaner energy sources to meet the rapid population and economic growth is more urgent than ever before. Being the most abundant carbon source in the atmosphere of Earth, CO2 can be used as an inexpensive C1 building block in the synthesis of aromatic fuels for internal combustion engines. We designed a process capable of synthesizing benzene, toluene, xylenes and mesitylene from CO2 and H2 at modest temperatures (T = 380 to 540 °C employing Fe/Fe3O4 nanoparticles as catalyst. The synthesis of the catalyst and the mechanism of CO2-hydrogenation will be discussed, as well as further applications of Fe/Fe3O4 nanoparticles in catalysis.

Mesitylene-Cored Glucoside Amphiphiles (MGAs) for Membrane Protein Studies: Importance of Alkyl Chain Density in Detergent Efficacy

DEFF Research Database (Denmark)

Cho, Kyung Ho; Ribeiro, Orquidea; Du, Yang

2016-01-01

Detergents serve as useful tools for membrane protein structural and functional studies. Their amphipathic nature allows detergents to associate with the hydrophobic regions of membrane proteins whilst maintaining the proteins in aqueous solution. However, widely used conventional detergents...

Development of Cold Neutron Scattering Kernels for Advanced Moderators

International Nuclear Information System (INIS)

Granada, J. R.; Cantargi, F.

2010-01-01

The development of scattering kernels for a number of molecular systems was performed, including a set of hydrogeneous methylated aromatics such as toluene, mesitylene, and mixtures of those. In order to partially validate those new libraries, we compared predicted total cross sections with experimental data obtained in our laboratory. In addition, we have introduced a new model to describe the interaction of slow neutrons with solid methane in phase II (stable phase below T = 20.4 K, atmospheric pressure). Very recently, a new scattering kernel to describe the interaction of slow neutrons with solid Deuterium was also developed. The main dynamical characteristics of that system are contained in the formalism, the elastic processes involving coherent and incoherent contributions are fully described, as well as the spin-correlation effects.

Effect of the environment on the electrical conductance of the single benzene-1,4-diamine molecule junction

Directory of Open Access Journals (Sweden)

Shigeto Nakashima

2011-11-01

Full Text Available We investigated the effect of the environment on the electrical conductance of a single benzene-1,4-diamine (BDA molecule bridging Au electrodes, using the scanning tunneling microscope (STM. The conductance of the single BDA molecule junction decreased upon a change in the environment from tetraglyme, to mesitylene, to water, and finally to N2 gas, while the spread in the conductance value increased. The order of the conductance values of the single BDA molecule junction was explained by the strength of the interaction between the solvent molecules and the Au electrodes. The order of the spread in the conductance values was explained by the diversity in the coverage of the BDA molecule at metal electrodes and atomic and molecular motion of the single-molecule junction.

Initial performance of the Cornell cold neutron beam

International Nuclear Information System (INIS)

Clark, D.D.; Spern, S.A.; Atwood, A.G.

1997-01-01

The cold source for a guided neutron beam has been installed in a Cornell TRIGA beamport and has successfully undergone thermal tests up to full power (normally 480 kW). Tests to date (8/1/96) include spectral and yield measurements at 10 kW with the first three meters of the 2-cm by 5-cm Ni-on-glass guide in place. A 110-cm 3 Al chamber, located 17 cm from the core, contains solid mesitylene and is cooled by conduction through a 269-cm long Cu rod connected to a cryorefrigerator outside the reactor shield. Distributions of flux per unit velocity have been measured at 10 kW by time-of-flight. Anticipated properties of the complete 13 m long beam at full power are discussed. (author)

Half-pseudoferrocene cations from nucleophilic addition of o-carboranyl anions to the [(eta(6)-mesitylene)(2)Fe](2+) dication

Czech Academy of Sciences Publication Activity Database

Bakardjiev, Mario; Štíbr, Bohumil; Holub, Josef; Růžička, A.; Padělková, Z.

2012-01-01

Roč. 41, č. 23 (2012), s. 7151-7155 ISSN 1477-9226 R&D Projects: GA ČR(CZ) GAP207/11/0705 Keywords : trialkylaluminum reagens * Iron complexes * reduction * biscarborane * B10C2H12 Subject RIV: CA - Inorganic Chemistry Impact factor: 3.806, year: 2012

Diluent and extractant effects on the enthalpy of extraction of uranium(VI) and americium(III) nitrates by trialkyl phosphates

International Nuclear Information System (INIS)

Srinivasan, T.G.; Vasudeva Rao, P.R.; Sood, D.D.

1998-01-01

The effect of various diluents such as n-hexane, n-heptane n-octane, isooctane, n-decane, n-undecane, n-dodecane, n-tetradecane, n-hexadecane, cyclohexane, benzene, toluene, p-xylene, mesitylene and o-dichlorobenzene on the enthalpy of extraction of uranyl nitrate by tri-n-amyl phosphate (TAP) over the temperature range 283 K--333 K has been studied. The results indicate that the enthalpy of extraction does not vary significantly with the diluents studied. Also enthalpies of extraction of uranyl nitrate and americium(III) nitrate by neutral organo phosphorous extractants such as tri-n-butyl phosphate (TBP), tri-n-amyl phosphate (TAP), tri-sec-butyl phosphate (TsBP), tri-isoamyl phosphate (TiAP) and tri-n-hexyl phosphate (THP) have been studied. An attempt has been made to explain the trends, on the basis of the nature of the solvate formed and the different terms which contribute to the overall enthalpy change

Design and safety aspects of the Cornell cold neutron source

International Nuclear Information System (INIS)

Ouellet, Carol G.; Clark, David D.

1992-01-01

The cold neutron beam facility at the Cornell University TRIGA Mark II reactor will begin operational testing in early 1993. It is designed to provide a low background subthermal neutron beam that is as free as possible of fast neutrons and gamma rays for applied research and graduate-level instruction. The Cornell cold neutron source differs from the more conventional types of cold sources in that it is inherently safer because it uses a safe handling material (mesitylene) as the moderator instead of hydrogen or methane, avoids the circulation of cryogenic fluids by removing heat from the system by conduction through a 99.99% pure copper rod attached to a cryogenic refrigerator, and is much smaller in its size and loads. The design details and potential hazards are described, where it is concluded that no credible accident involving the cold source could cause damage to the reactor or personnel, or cause release of radioactivity. (author)

Grafting cavitands on the Si(100) surface.

Science.gov (United States)

Condorelli, Guglielmo G; Motta, Alessandro; Favazza, Maria; Fragalà, Ignazio L; Busi, Marco; Menozzi, Edoardo; Dalcanale, Enrico; Cristofolini, Luigi

2006-12-19

Cavitand molecules having double bond terminated alkyl chains and different bridging groups at the upper rim have been grafted on H-terminated Si(100) surface via photochemical hydrosilylation of the double bonds. Pure and mixed monolayers have been obtained from mesitylene solutions of either pure cavitand or cavitand/1-octene mixtures. Angle resolved high-resolution X-ray photoelectron spectroscopy has been used as the main tool for the monolayer characterization. The cavitand decorated surface consists of Si-C bonded layers with the upper rim at the top of the layer. Grafting of pure cavitands leads to not-well-packed layers, which are not able to efficiently passivate the Si(100) surface. By contrast, monolayers obtained from cavitand/1-octene mixtures consist of well-packed layers since they prevent silicon oxidation after aging. AFM measurements showed that these monolayers have a structured topography, with objects protruding from the Si(100) surface with average heights compatible with the expected ones for cavitand molecules.

Hydrogenation of Isophthalonitrile with 1-Methylimidazole as an Effective Solvent for m-Xylenediamine Production

Energy Technology Data Exchange (ETDEWEB)

Chae, Tae Young; Row, Sung Wook; Yoo, Kye Sang; Lee, Sang Duek [Environment and Process Technology Division, Seoul (Korea, Republic of); Lee, Do Weon [University of Seoul, Seoul (Korea, Republic of)

2006-03-15

1-methylimidazole was shown to outperform the other organic solvents in this reaction. Moreover, amount of ammonia with using 1-methylimidazole as a solvent was lower than other processes. Thus, 1-methylimidazole is an attractive solvent in IPN hydrogenation for the production of MXDA. The correct choice of a solvent is a critical factor to govern the catalytic activity with desirable hydrogenation. Conventionally, organic materials such as aromatic hydrocarbons, aliphatic alcohols, aliphatic hydrocarbons, dimethylformamide and dioxane were employed in this reaction. Several MXDA producing processes with the organic solvent including m-xylene, pseudocumene, mesitylene, ethylbenzene, methylpyridine, benzonitrile, m-tolunitrile, MXDA and cyanopyridine were disclosed. However, the solvents and ammonia were vaporized under the operation conditions leading to amine cleavage with the resulting formation of methylbenzyl amines or the consumption of ammonia was still significant. Recently, some researchers reported that a high yield of MXDA was achieved using isopropanol under relatively low pressure condition; however, the consumption of ammonia was very significant.

Formation of highly oxygenated organic molecules from aromatic compounds

Science.gov (United States)

Molteni, Ugo; Bianchi, Federico; Klein, Felix; El Haddad, Imad; Frege, Carla; Rossi, Michel J.; Dommen, Josef; Baltensperger, Urs

2018-02-01

Anthropogenic volatile organic compounds (AVOCs) often dominate the urban atmosphere and consist to a large degree of aromatic hydrocarbons (ArHCs), such as benzene, toluene, xylenes, and trimethylbenzenes, e.g., from the handling and combustion of fuels. These compounds are important precursors for the formation of secondary organic aerosol. Here we show that the oxidation of aromatics with OH leads to a subsequent autoxidation chain reaction forming highly oxygenated molecules (HOMs) with an O : C ratio of up to 1.09. This is exemplified for five single-ring ArHCs (benzene, toluene, o-/m-/p-xylene, mesitylene (1,3,5-trimethylbenzene) and ethylbenzene), as well as two conjugated polycyclic ArHCs (naphthalene and biphenyl). We report the elemental composition of the HOMs and show the differences in the oxidation patterns of these ArHCs. A potential pathway for the formation of these HOMs from aromatics is presented and discussed. We hypothesize that AVOCs may contribute substantially to new particle formation events that have been detected in urban areas.

A three-dimensional metal–organic framework for selective sensing of nitroaromatic compounds

Directory of Open Access Journals (Sweden)

Dan Tian

2014-12-01

Full Text Available A 3D metal–organic framework [NH2(CH32][Cd6(L4(DMF6(HCOO](DMF = N,N-dimethylformamide (1 has been synthesized using a tripodal ligand H3L (2,4,6-tris[1-(3-carboxylphenoxyylmethyl]mesitylene. The obtained complex exhibits a 3D framework containing hexanuclear {Cd6} building units formed by two trinuclear {Cd3} clusters that are connected via HCOO− anions. For complex 1, the participation of the fluorescent ligand H3L not only gives rise to a strong photoluminescence emission as expected, but more interestingly, that ligand originated characteristic band could be quenched selectively by nitrobenzene with a low detection limit, showing its potential as a highly sensitive and selective sensor for nitrobenzene. Based on an electron transfer quenching mechanism, the fluorescence sensing ability of 1 is also applicable for other electron-deficient nitroaromatic compounds with high selectivity and sensitivity, i.e., 1,4-dinitrobenzene, 1,3-dinitrobenzene, 2,4-dinitrotoluene, and 4-nitrotoluene, suggesting 1 a promising fluorescence sensor for detecting and recognizing the same kind of chemicals.

Formation of highly oxygenated organic molecules from aromatic compounds

Directory of Open Access Journals (Sweden)

U. Molteni

2018-02-01

Full Text Available Anthropogenic volatile organic compounds (AVOCs often dominate the urban atmosphere and consist to a large degree of aromatic hydrocarbons (ArHCs, such as benzene, toluene, xylenes, and trimethylbenzenes, e.g., from the handling and combustion of fuels. These compounds are important precursors for the formation of secondary organic aerosol. Here we show that the oxidation of aromatics with OH leads to a subsequent autoxidation chain reaction forming highly oxygenated molecules (HOMs with an O : C ratio of up to 1.09. This is exemplified for five single-ring ArHCs (benzene, toluene, o-/m-/p-xylene, mesitylene (1,3,5-trimethylbenzene and ethylbenzene, as well as two conjugated polycyclic ArHCs (naphthalene and biphenyl. We report the elemental composition of the HOMs and show the differences in the oxidation patterns of these ArHCs. A potential pathway for the formation of these HOMs from aromatics is presented and discussed. We hypothesize that AVOCs may contribute substantially to new particle formation events that have been detected in urban areas.

Chemical Composition and Aroma Evaluation of Essential Oils from Skunk Cabbage (Symplocarpus foetidus).

Science.gov (United States)

Miyazawa, Mitsuo; Nakahashi, Hiroshi; Kashima, Yusei; Motooka, Ryota; Hara, Nobuyuki; Nakagawa, Hiroki; Yoshii, Takashi; Usami, Atsushi; Marumoto, Shinsuke

2015-01-01

Two sample preparation methods, namely hydrodistillation (HD) and solvent-assisted flavor evaporation (SAFE), have been used to investigate the essential oils of the aerial parts (leaves and stems) of Symplocarpus foetidus, a plant with a characteristic odor, by gas chromatography mass spectrometry (GC-MS). Characteristic aroma-active compounds in the oils were detected by GC-Olfactometry (GC-O) and aroma extract dilution analysis (AEDA). From the HD method, the main compounds in the oil were found to be p-vinyl-guaiacol (15.5%), 2-pentyl-furan (13.4%), and (Z)-ligustilide (9.5%). From the SAFE method, the main compounds were 2-butoxy-ethanol (49.6%), ethyl-pentanoate (4.5%), and mesitylene (4.0%). In HD oil, the most intense aroma-active compounds were 2-pentyl-furan (flavor dilution factor (FD) = 32, odor activity value (OAV) = 57), p-vinyl-guaiacol (FD = 16, OAV = 41), and dimethyl disulfide (FD = 16, OAV = 41). In SAFE oil, the main aroma-active compounds were 2-butoxy ethanol (FD = 32, OAV = 16), and 2-methoxy thiazole (FD = 32, OAV = 25).

High pressure study of viscosity effects on the luminescence of tetracyanobenzene EDA complexes

Science.gov (United States)

Thomas, Michele Moisio; Drickamer, H. G.

1981-03-01

High pressure fluorescence studies fron 0-10 kbar have been performed on electron donor-acceptor (EDA) complexes of s-tetracyanobenzene (TCNB) with a series of aromatic hydrocarbons. Four solvents were used, 2,2,4,4,6,8,8 heptamethylnonane (HMN), methylcyclohexane (MCH), 2,6,10,14 tetramethylpentadecane (TMPD), and a mixture of MCH and HMN. A viscosity range from 0.006 to 10 000 poise was covered at constant temperature. As pressure (viscosity) increased the fluorescence spectrum shifted from one dominated by emission from the equilibrium (EQ) excited singlet state to one dominated by Franck-Condon (FC) singlet emission. Lifetime measurements for the complexes of o-xylene and p-xylene with TCNB as well as one mesitylene complex yielded the two radiative rates (kEQ and kFC) as well as the rate of internal conversion from FC to the EQ excited state to (kIC). The results are discussed in terms of the rate of relaxation of the solvent compared with the rate kFC. It was found that kIC correlated very well with the solvent viscosity.

A three-dimensional metal–organic framework for selective sensing of nitroaromatic compounds

Energy Technology Data Exchange (ETDEWEB)

Tian, Dan; Chen, Rong-Ying; Xu, Jian; Bu, Xian-He, E-mail: buxh@nankai.edu.cn [Department of Chemistry, Collaborative Innovation Center of Chemical Science and Engineering, and Tianjin Key Lab of Metal and Molecule-based Material Chemistry, Nankai University, Tianjin 300071 (China); Li, Yun-Wu [Department of Chemistry, Collaborative Innovation Center of Chemical Science and Engineering, and Tianjin Key Lab of Metal and Molecule-based Material Chemistry, Nankai University, Tianjin 300071 (China); School of Chemistry and Chemical Engineering and Shandong Provincial Key Laboratory of Chemical Energy Storage and Novel Cell Technology, Liaocheng University, Liaocheng 252000 (China)

2014-12-01

A 3D metal–organic framework [NH{sub 2}(CH{sub 3}){sub 2}][Cd{sub 6}(L){sub 4}(DMF){sub 6}(HCOO)](DMF = N,N-dimethylformamide) (1) has been synthesized using a tripodal ligand H{sub 3}L (2,4,6-tris[1-(3-carboxylphenoxy)ylmethyl]mesitylene). The obtained complex exhibits a 3D framework containing hexanuclear (Cd{sub 6}) building units formed by two trinuclear (Cd{sub 3}) clusters that are connected via HCOO{sup −} anions. For complex 1, the participation of the fluorescent ligand H{sub 3}L not only gives rise to a strong photoluminescence emission as expected, but more interestingly, that ligand originated characteristic band could be quenched selectively by nitrobenzene with a low detection limit, showing its potential as a highly sensitive and selective sensor for nitrobenzene. Based on an electron transfer quenching mechanism, the fluorescence sensing ability of 1 is also applicable for other electron-deficient nitroaromatic compounds with high selectivity and sensitivity, i.e., 1,4-dinitrobenzene, 1,3-dinitrobenzene, 2,4-dinitrotoluene, and 4-nitrotoluene, suggesting 1 a promising fluorescence sensor for detecting and recognizing the same kind of chemicals.

Cryogenic engineering and thermometry for an in-core apparatus

International Nuclear Information System (INIS)

Clark, D.D.; Spern, S.A.; Atwood, A.G.; Ouellet, C.G.; Decker, F.H.

1996-01-01

During the design, construction, and testing of the final model of the cold neutron source for the cold neutron beam facility of the Cornell TRIGA reactor, several interesting cryogenic and thermometric problems were encountered. This paper summarizes some of those problems and their solutions. The goal is to maintain an aluminum chamber containing 110cm 3 of mesitylene at 30 K or below in the presence of radiation fields of 1 x 10 12 thermal n/cm 2 · s, 3.8 x 10 10 fast n/cm 2 · s, and 1.4 x 10 3 rad/s of gamma rays known to exist at 500 kW within the beam port 17 cm from the core edge. Cooling is accomplished by conduction through a 1.85-cm-diam, 261-cm-long copper rod connecting the chamber to a two-stage Gifford-McMahon cryorefrigerator located outside the reactor bulk shield. It is desirable to measure the temperatures of the chamber, the refrigerator, and a number of other system components for monitoring and diagnostic purposes. The principal concerns are the heat loads and radiation effects caused by the nuclear radiation

Polymethylated [Fe(η6-arene)2]2+ dications: methyl-group rearrangements and application of the EINS mechanism.

Science.gov (United States)

Štíbr, Bohumil; Bakardjiev, Mario; Hájková, Zuzana; Holub, Josef; Padělková, Zdenka; Růžička, Aleš; Kennedy, John D

2011-06-14

Reactions between the methylated arenes ArMe(n) [where ArMe(n) = C(6)Me(n)H((6-n)), and n = 1-6] and FeCl(2) in heptane at 90 °C in the presence of anhydrous AlCl(3) give, for the arenes with n = 1-5, extensive isomerisations and disproportionations involving the methyl groups on the arene rings, and the formation of mixtures of [Fe(ArMe(n))(2)](2+) dications that defy separation into pure species. GC-MS studies of AlCl(3)/mesitylene and AlCl(3)/durene reactions in the absence of FeCl(2) (90 °C, 2 h) allow quantitative assessments of the rearrangements, and the EINS mechanism (electrophile-induced nucleophilic substitution) is applied to rationalise the phenomena. By contrast, ArMe(n) / FeCl(2) /AlCl(3) reactions in heptane for 24-36 h at room-temperature proceed with no rearrangements, allowing the synthesis of the complete series of pure [Fe(ArMen)](2+) cations in yields of 48-71%. The pure compounds are characterised by (1)H NMR spectroscopy and electrospray-ionization mass-spectrometry (ESI-MS), and the structures of [Fe(m-xylene)(2)][PF(6)](2) and [Fe(durene)(2)][PF(6)](2) are established by single-crystal X-ray diffraction analyses.

Formation and determination of perinaphthenyl radical and PCAH in combustion processes

Energy Technology Data Exchange (ETDEWEB)

Franceschi, A [Univ., Pisa, Italy; Gerbaz, G P; Mangolini, S

1976-09-01

The concentration profiles of polycyclic aromatic hydrocarbons (PCAH) and perinaphthenyl radical along a vertical flow reactor have been determined for fuel rich premixed flames of n-heptane with small fractions of other hydrocarbons, methanol, and nitrogen oxide. It has been found that there is a strict relation between the concentrations of the higher molecular weight PCAH, which are the main components of soluble fraction of soot, and the perinaphthenyl radical. The aromatic ring of the fuel supplying the reactor plays the most significant role in the formation of PCAH and perinaphthenyl radical. Furthermore their concentrations increase passing from benzene toluene and, lastly, to mesitylene, because the energy of the C(arom)--C(alif) bond is lower than that of the C(arom)--C(arom) bond. The promoting action of methanol, when added to benzene, in the formation of PCAH and perinaphthenyl radical could be explained by the increased presence of CH/sub 3/ . radicals, which, can overcome the inhibiting action of OH. radicals. The contrary happens when methanol is added to toluene, because CH/sub 3/. coming from alcohol represents only a small fraction of the overall concentration, while the oxidant activity of OH. is prevailing. Finally the strong action of NO in reducing the free radical concentration has been pointed out.

A review and assessment of hydrodynamic cavitation as a technology for the future.

Science.gov (United States)

Gogate, Parag R; Pandit, Aniruddha B

2005-01-01

In the present work, the current status of the hydrodynamic cavitation reactors has been reviewed discussing the bubble dynamics analysis, optimum design considerations, design correlations for cavitational intensity (in terms of collapse pressure)/cavitational yield and different successful chemical synthesis applications clearly illustrating the utility of these types of reactors. The theoretical discussion based on the modeling of the bubble dynamics equations aims at understanding the design information related to the dependency of the cavitational intensity on the operating parameters and recommendations have been made for the choice of the optimized conditions of operating parameters. The design information based on the theoretical analysis has also been supported with some experimental illustrations concentrating on the chemical synthesis applications. Assessment of the hydrodynamic cavitation reactors and comparison with the sonochemical reactors has been done by citing the different industrially important reactions (oxidation of toluene, o-xylene, m-xylene, p-xylene, mesitylene, o-nitrotoluene, p-nitrotoluene, m-nitrotoluene, o-chlorotoluene and p-chlorotoulene, and trans-esterification reaction i.e., synthesis of bio-diesel). Some recommendations have also been made for the future work to be carried out as well as the choice of the operating conditions for realizing the dream of industrial scale applications of the cavitational reactors.

Effect of the Amide Bond Diamine Structure on the CO 2 , H 2 S, and CH 4 Transport Properties of a Series of Novel 6FDA-Based Polyamide–Imides for Natural Gas Purification

KAUST Repository

Vaughn, J.

2012-09-11

A series of higher permeability polyamide-imides based on 2,2′-bis(3,4-dicarboxyphenyl) hexafluoropropane dianhydride with comparable plasticization resistance to Torlon were synthesized and formed into dense film membranes. Polymers possessing 2,4-diamino mesitylene (DAM) were stable up to 56 atm of pure CO 2, which is due to enhanced charge transfer complex formation compared to polymers containing 4,4′- (hexafluoroisopropylidene) dianiline (6FpDA) and 2,3,5,6-tetramethyl-1,4- phenylenediamine (TmPDA). The new polymers containing DAM and TmPDA showed ideal CO 2/CH 4 selectivities of near 50 with CO 2 and H 2S permeabilities over an order of magnitude higher than Torlon. CO 2 and CH 4 sorption in the DAM- and TmPDA-based materials was reduced, whereas H 2S sorption was enhanced relative to membranes containing fluorinated 6FpDA. Consequently, DAM- and TmPDA-based membranes showed increased stability toward high pressure CO 2 but lower plasticization resistance toward pure H 2S. These results highlight the differences between CO 2 and H 2S that challenge the rational design of materials targeting simultaneous separation of both contaminants. © 2012 American Chemical Society.

Pressure and solvent shifts of charge transfer absorption band of iodine complexes

International Nuclear Information System (INIS)

Sawamura, Seiji; Taniguchi, Yoshihiro; Suzuki, Keizo

1979-01-01

Absorption spectra of the CT band of I 2 complexes were observed in several nonpolar solvents at 1 bar, and in heptane up to 4400 bar. All solvent shifts were red with an increase in (n 2 - 1)/(2n 2 + 1), the refractive index (n) function of solvents, consistent with the solvent shift theory. On the other hand pressure caused a variety of shifts, that is, red shifts in benzene-, toluene-, and mesitylene-I 2 complexes, an inversion shift from red to blue in HMB-I 2 complex, and blue shifts in Et 3 N-, n-Pr 3 N-, and n-Bu 3 N-I 2 complexes, though increase in pressure invariably raises the (n 2 - 1)/(2n 2 + 1) value of solvent. The pressure shifts of I 2 complexes seem to be interpreted by a sum of two effects. One is the increased polarity of the solvent, which causes a red shift. The other is the decrease in the bond distance between a donor and an acceptor, which contributes to a blue shift in a strong CT complex and to a red shift in a week one. The pressure and solvent shifts of I 2 complexes were compared with those of π-donor-TCNE complexes. (author)

Deuterium isotope effects during formation of phenols by hepatic monoxygenases. Evidence for an alternative to the arene oxide pathway

International Nuclear Information System (INIS)

Tomaszewski, J.E.; Jerina, D.M.; Daly, J.W.

1975-01-01

The in vivo and in vitro metabolisms of normal and deuterated aromatic substrates have been investigated in rats. Significant isotope effects (k/ sub H//k/sub D/ equals 1.3-1.75) were associated with in vivo formation of meta-hydroxylated metabolites from 1:1 mixtures of normal and perdeuterio-(arylring) nitrobenzene, methyl phenyl sulfide, and methyl phenyl sulfone. Since isotope effects of this magnitude are incompatible with arene oxides as intermediates in the formation of phenols, the results provide evidence that multiple pathways are responsible for the formation of phenols in mammals. Significant isotope effects were not associated with the formation of the other phenolic isomers of nitrobenzene, methyl phenyl sulfone, or methyl phenyl sulfide or with the formation of phenolic products from anisole, bromobenzene, chlorobenzene, fluorobenzene, benzonitrile, naphthalene, zoxazolamine, acetanilide, biphenyl, diphenylhydantoin, benzene, o- and p-xylene, toluene, and mesitylene. Significant isotope effects might not be observable with the latter substrates if the kinetic parameters for oxidation of substrate change or if the arene oxide pathway greatly predominates. Furthermore, extensive in vivo metabolism of any substrate would make isotope effects unobservable by the procedure employed, namely the analysis of isotope content in metabolites formed from 1:1 mixtures of normal and deuterated substrates. (U.S.)

The University of Texas Cold Neutron Source

International Nuclear Information System (INIS)

Uenlue, Kenan; Rios-Martinez, Carlos; Wehring, B.W.

1994-01-01

A cold neutron source has been designed, constructed, and tested by the Nuclear Engineering Teaching Laboratory (NETL) at The University of Texas at Austin. The Texas Cold Neutron Source (TCNS) is located in one of the beam ports of the NETL 1-MW TRIGA Mark II research reactor. The main components of the TCNS are a cooled moderator, a heat pipe, a cryogenic refrigerator, and a neutron guide. 80 ml of mesitylene moderator are maintained at about 30 K in a chamber within the reactor graphite reflector by the heat pipe and cryogenic refrigerator. The heat pipe is a 3-m long aluminum tube that contains neon as the working fluid. The cold neutrons obtained from the moderator are transported by a curved 6-m long neutron guide. This neutron guide has a radius of curvature of 300 m, a 50x15 mm cross-section, 58 Ni coating, and is separated into three channels. The TCNS will provide a low-background subthermal neutron beam for neutron capture and scattering research. After the installation of the external portion of the neutron guide, a neutron focusing system and a Prompt Gamma Activation Analysis facility will be set up at the TCNS. ((orig.))

Core-Shell Diamond as a Support for Solid-Phase Extraction and High-Performance Liquid Chromatography

Energy Technology Data Exchange (ETDEWEB)

Saini, Gaurav; Jensen, David S.; Wiest, Landon A.; Vail, Michael A.; Dadson, Andrew; Lee, Milton L.; Shutthanandan, V.; Linford, Matthew R.

2010-06-01

We report the formation of core-shell diamond particles for solid phase extraction (SPE) and high performance liquid chromatography (HPLC) made by layer-by-layer (LbL) deposition. Their synthesis begins with the amine functionalization of microdiamond by its immersion in an aqueous solution of a primary amine-containing polymer (polyallylamine (PAAm)). The amine-terminated microdiamond is then immersed in an aqueous suspension of nanodiamond, which leads to adsorption of the nanodiamond. Alternating (self-limiting) immersions in the solutions of the amine-containing polymer and the suspension of nanodiamond are continued until the desired number of nanodiamond layers is formed around the microdiamond. Finally, the core-shell particles are cross-linked with 1,2,5,6-diepoxycyclooctane or reacted with 1,2-epoxyoctadecane. Layer-by-layer deposition of PAAm and nanodiamond is also studied on planar Si/SiO2 surfaces, which were characterized by SEM, Rutherford backscattering spectrometry (RBS) and nuclear reaction analysis (NRA). Core-shell particles are characterized by diffuse reflectance infrared Fourier transform spectroscopy (DRIFT), environmental scanning electron microscopy (ESEM), and Brunauer Emmett Teller (BET) surface area and pore size measurements. Larger (ca. 50 μm) core-shell diamond particles have much higher surface areas, and analyte loading capacities in SPE than nonporous solid diamond particles. Smaller (ca. 3 μm), normal and reversed phase, core-shell diamond particles have been used for HPLC, with 36,300 plates per meter for mesitylene in a separation of benzene and alkyl benzenes on a C18 adsorbent, and 54,800 plates per meter for diazinon in a similar separation of two pesticides.

Core-shell diamond as a support for solid-phase extraction and high-performance liquid chromatography.

Science.gov (United States)

Saini, Gaurav; Jensen, David S; Wiest, Landon A; Vail, Michael A; Dadson, Andrew; Lee, Milton L; Shutthanandan, V; Linford, Matthew R

2010-06-01

We report the formation of core-shell diamond particles for solid-phase extraction (SPE) and high-performance liquid chromatography (HPLC) made by layer-by-layer (LbL) deposition. Their synthesis begins with the amine functionalization of microdiamond by its immersion in an aqueous solution of a primary amine-containing polymer (polyallylamine (PAAm)). The amine-terminated microdiamond is then immersed in an aqueous suspension of nanodiamond, which leads to adsorption of the nanodiamond. Alternating (self-limiting) immersions in the solutions of the amine-containing polymer and the suspension of nanodiamond are continued until the desired number of nanodiamond layers is formed around the microdiamond. Finally, the core-shell particles are cross-linked with 1,2,5,6-diepoxycyclooctane or reacted with 1,2-epoxyoctadecane. Layer-by-layer deposition of PAAm and nanodiamond is also studied on planar Si/SiO(2) surfaces, which were characterized by scanning electron microscopy (SEM), Rutherford backscattering spectrometry (RBS), and nuclear reaction analysis (NRA). Core-shell particles are characterized by diffuse reflectance infrared Fourier transform spectroscopy (DRIFT), environmental scanning electron microscopy (ESEM), and Brunauer-Emmett-Teller (BET) surface area and pore size measurements. Larger (ca. 50 microm) core-shell diamond particles have much higher surface areas and analyte loading capacities in SPE than nonporous solid diamond particles. Smaller (ca. 3 microm), normal and reversed-phase, core-shell diamond particles have been used for HPLC, with 36,300 plates/m for mesitylene in a separation of benzene and alkyl benzenes and 54,800 plates/m for diazinon in a similar separation of two pesticides on a C(18) adsorbent.

Core-Shell Diamond as a Support for Solid-Phase Extraction and High-Performance Liquid Chromatography

International Nuclear Information System (INIS)

Saini, Gaurav; Jensen, David S.; Wiest, Landon A.; Vail, Michael A.; Dadson, Andrew; Lee, Milton L.; Shutthanandan, V.; Linford, Matthew R.

2010-01-01

We report the formation of core-shell diamond particles for solid phase extraction (SPE) and high performance liquid chromatography (HPLC) made by layer-by-layer (LbL) deposition. Their synthesis begins with the amine functionalization of microdiamond by its immersion in an aqueous solution of a primary amine-containing polymer (polyallylamine (PAAm)). The amine-terminated microdiamond is then immersed in an aqueous suspension of nanodiamond, which leads to adsorption of the nanodiamond. Alternating (self-limiting) immersions in the solutions of the amine-containing polymer and the suspension of nanodiamond are continued until the desired number of nanodiamond layers is formed around the microdiamond. Finally, the core-shell particles are cross-linked with 1,2,5,6-diepoxycyclooctane or reacted with 1,2-epoxyoctadecane. Layer-by-layer deposition of PAAm and nanodiamond is also studied on planar Si/SiO2 surfaces, which were characterized by SEM, Rutherford backscattering spectrometry (RBS) and nuclear reaction analysis (NRA). Core-shell particles are characterized by diffuse reflectance infrared Fourier transform spectroscopy (DRIFT), environmental scanning electron microscopy (ESEM), and Brunauer Emmett Teller (BET) surface area and pore size measurements. Larger (ca. 50 ?m) core-shell diamond particles have much higher surface areas, and analyte loading capacities in SPE than nonporous solid diamond particles. Smaller (ca. 3 ?m), normal and reversed phase, core-shell diamond particles have been used for HPLC, with 36,300 plates per meter for mesitylene in a separation of benzene and alkyl benzenes on a C18 adsorbent, and 54,800 plates per meter for diazinon in a similar separation of two pesticides.

Selective Complexation of Cyanide and Fluoride Ions with Ammonium Boranes: A Theoretical Study on Sensing Mechanism Involving Intramolecular Charge Transfer and Configurational Changes.

Science.gov (United States)

Bhat, Haamid R; Jha, Prakash C

2017-05-18

The anion binding selectivity and the recognition mechanism of two isomeric boranes, namely, 4-[bis(2,4,6-trimethylphenyl)boranyl]-N,N,N-trimethylaniline ([p-(Mes 2 B)C 6 H 4 (NMe 3 )] + , 1, where "Mes" represents mesitylene and "Me" represents methyl) and 2-[bis(2,4,6-trimethylphenyl)boranyl]-N,N,N-trimethylaniline ([o-(Mes 2 B)C 6 H 4 (NMe 3 )] + , 2) has been investigated using density functional theory (DFT) and time dependent-density functional theory (TD-DFT) methods. Natural population analysis indicates that the central boron atoms in 1 and 2 are the most active centers for nucleophilic addition of anions. The negative magnitude of free energy changes (ΔG) reveals that out of CN - , F - , Cl - , Br - , NO 3 - , and HSO 4 - only the binding of CN - and F - with 1 and 2 is thermodynamically feasible and spontaneous. In addition, the calculated binding energies reveal that the CN - is showing lesser binding affinity than F - both with 1 and 2, while other ions, viz. NO 3 - , HSO 4 - , Br - , and Cl - , either do not bind at all or show very insignificant binding energy. The first excited states (S 1 ) of 1 and 2 are shown to be the local excited states with π → σ* transition by frontier molecular orbital analysis, whereas fourth excited states (S 4 ) of 4-[bis(2,4,6-trimethylphenyl)boranyl]-N,N,N-trimethylaniline cyanide ([p-(Mes 2 B)C 6 H 4 (NMe 3 )] CN, 1CN, the cyano form of 1) and 4-[bis(2,4,6-trimethylphenyl)boranyl]-N,N,N-trimethylaniline fluoride ([p-(Mes 2 B)C 6 H 4 (NMe 3 )] F, 1F, the fluoro form of 1) and fifth excited state (S 5 ) of 2-[bis(2,4,6-trimethylphenyl)boranyl]-N,N,N-trimethylaniline fluoride ([o-(Mes 2 B)C 6 H 4 (NMe 3 )] F, 2F, the fluoro form of 2) are charge separation states that are found to be responsible for the intramolecular charge transfer (ICT) process. The synergistic effect of ICT and partial configuration changes induce fluorescence quenching in 1CN, 1F, and 2F after a significant internal conversion (IC) from S 4 and

Kinetic isotope effects and tunnelling in the proton-transfer reaction between 4-nitrophenylnitromethane and tetramethylguanidine in various aprotic solvents

International Nuclear Information System (INIS)

Caldin, E.F.; Mateo, S.

1975-01-01

Rates and equilibrium constants have been determined for the proton-transfer reaction of 4-nitrophenylnitromethane, NO 2 C 6 H 4 CH 2 NO 2 , and its αα-deuterated analogue NO 2 C 6 H 4 CD 2 NO 2 , with the strong base tetramethylguanidine [HN=C(NMe 2 ) 2 ), at temperatures between -60 0 C and +65 0 in a range of aprotic solvents. Spectrophotometry and the stopped-flow technique were used. The reaction is a simple proton-transfer process leading to an ion-pair. The kinetic isotope effects are correlated with the polarity of the solvents, as measured by the dielectric constant or by the empirical parameter Esub(T). In the less polar solvents they are exceptionally large. In toluene, for example, at 25 0 C the rate ratio ksup(H)/ksup(D) = 45 +- 2, the activation energy difference Esub(a)sup(D) - Esub(a)sup(H) =4.3 +- 0.3 kcal molsup(-1) (16 kJ molsup(-1), and the ratio of the pre-exponential factors logsub(10) (Asup(D)/Asup(H)) = 1.5 +- 0.2+ and even larger values of logsub(10)(Asup(D)/Asup(H)) are found for mesitylene (1.94 +- 0.06) and cyclohexane (2.4 +- 0.2). Positive deviations from linear Arrhenius plots are found for these solvents. Tunnelling is the only interpretation that cannot account for these results. For the more polar solvents (dielectric constant 7 to 37), the isotope effects are closer to the range predicted by semi-classical theory. The isotope effects in all solvents have been fitted to Bell's equation for a parabolic barrier, and the barrier dimensions calculated for each solvent. The suggested interpretation of the results is that the solvent-solute interactions affect the height of the barrier and that motions of solvent molecules are coupled with the motion of the proton in the more polar solvents but not in the less polar ones; reorganization of solvent molecules accompanies the proton-transfer in the more polar solvents, but only electron-polarization in the less polar. Tunnelling has large effects in the less polar solvents, where the

Interconversion of η3-H2SiRR' σ-complexes and 16-electron silylene complexes via reversible H-H or C-H elimination.

Science.gov (United States)

Lipke, Mark C; Neumeyer, Felix; Tilley, T Don

2014-04-23

Solid samples of η(3)-silane complexes [PhBP(Ph)3]RuH(η(3)-H2SiRR') (R,R' = Et2, 1a; PhMe, 1b; Ph2, 1c, MeMes, 1d) decompose when exposed to dynamic vacuum. Gas-phase H2/D2 exchange between isolated, solid samples of 1c-d3 and 1c indicate that a reversible elimination of H2 is the first step in the irreversible decomposition. An efficient solution-phase trap for hydrogen, the 16-electron ruthenium benzyl complex [PhBP(Ph)3]Ru[η(3)-CH2(3,5-Me2C6H3)] (3) reacts quantitatively with H2 in benzene via elimination of mesitylene to form the η(5)-cyclohexadienyl complex [PhBP(Ph)3]Ru(η(5)-C6H7) (4). This H2 trapping reaction was utilized to drive forward and quantify the elimination of H2 from 1b,d in solution, which resulted in the decomposition of 1b,d to form 4 and several organosilicon products that could not be identified. Reaction of {[PhBP(Ph)3]Ru(μ-Cl)}2 (2) with (THF)2Li(SiHMes2) forms a new η(3)-H2Si species [PhBP(Ph)3]Ru[CH2(2-(η(3)-H2SiMes)-3,5-Me2C6H2)] (5) which reacts with H2 to form the η(3)-H2SiMes2 complex [PhBP(Ph)3]RuH(η(3)-H2SiMes2) (1e). Complex 1e was identified by NMR spectroscopy prior to its decomposition by elimination of Mes2SiH2 to form 4. DFT calculations indicate that an isomer of 5, the 16-electron silylene complex [PhBP(Ph)3]Ru(μ-H)(═SiMes2), is only 2 kcal/mol higher in energy than 5. Treatment of 5 with XylNC (Xyl = 2,6-dimethylphenyl) resulted in trapping of [PhBP(Ph)3]Ru(μ-H)(═SiMes2) to form the 18-electron silylene complex [PhBP(Ph)3]Ru(CNXyl)(μ-H)(═SiMes2) (6). A closely related germylene complex [PhBP(Ph)3]Ru[CN(2,6-diphenyl-4-MeC6H2)](H)(═GeH(t)Bu) (8) was prepared from reaction of (t)BuGeH3 with the benzyl complex [PhBP(Ph)3]Ru[CN(2,6-diphenyl-4-MeC6H2)][η(1)-CH2(3,5-Me2C6H3)] (7). Single crystal XRD analysis indicated that unlike for 6, the hydride ligand in 8 is a terminal hydride that does not engage in 3c-2e Ru-H → Ge bonding. Complex 1b is an effective precatalyst for the catalytic Ge-H dehydrocoupling

NOCHAR Polymers: An Aqueous and Organic Liquid Solidification Process for Cadarache LOR (Liquides Organiques Radioactifs) - 13195

International Nuclear Information System (INIS)

Vaudey, Claire-Emilie; Renou, Sebastien; Porco, Julien; Kelley, Dennis; Cochaud, Chantal; Serrano, Roger

2013-01-01

To handle the Very Low Level Waste (VLLW) and the Low Level Waste (LLW) in France, two options can be considered: the incineration at CENTRACO facility and the disposal facility on ANDRA sites. The waste acceptance in these radwaste routes is dependent upon the adequacy between the waste characteristics (physical chemistry and radiological) and the radwaste route specifications. If the waste characteristics are incompatible with the radwaste route specifications (presence of significant quantities of chlorine, fluorine, organic component etc or/and high activity limits), it is necessary to find an alternative solution that consists of a waste pre-treatment process. In the context of the problematic Cadarache LOR (Liquides Organiques Radioactifs) waste streams, two radioactive scintillation cocktails have to be treated. The first one is composed of organic liquids at 13.1 % (diphenyloxazol, mesitylene, TBP, xylene) and water at 86.9 %. The second one is composed of TBP at 8.6 % and water at 91.4 %. They contain chlorine, fluorine and sulphate and have got alpha/beta/gamma spectra with mass activities equal to some kBq.g -1 . Therefore, tritium is present and creates the second problematic waste stream. As a consequence, in order for disposal acceptance at the ANDRA site, it is necessary to pre-treat the waste. The NOCHAR polymers as an aqueous and organic liquid solidification process seem to be an adequate solution. Indeed, these polymers constitute an important variety of products applied to the treatment of radioactive aqueous and organic liquids (solvent, oil, solvent/oil mixing etc) and sludge through a mechanical and chemical solidification process. For Cadarache LOR, N910 and N960 respectively dedicated to the organic and aqueous liquids solidification are considered. With the N910, the organic waste solidification occurs in two steps. As the organic liquid travels moves through the polymer strands, the strands swell and immobilise the liquid. Then as the

Cadarache LOR (liquides organiques radioactifs) treatment by a solidification process using NOCHAR polymers

International Nuclear Information System (INIS)

Vaudey, Claire-Emilie; Renou, Sebastien; Kelley, Dennis; Cochaud, Chantal; Serrano, Roger

2013-01-01

In France, two options can be considered to handle the Very Low Level Waste (VLLW) and the Low Level Waste (LLW). The first one is the incineration at CENTRACO facility and the second one is the disposal at ANDRA sites. The waste acceptance in these two channels is dependent upon the adequacy between the waste characteristics (physical chemistry and radiological) and the channel specifications. If the waste characteristics and the channel specifications (presence of significant quantities of halogens, complexing agents, organic components... or/and high activity limits) are incompatible, an alternative solution have to be identify. It consists of a waste pre-treatment process. For Cadarache LOR (Liquides Organiques Radioactifs) waste streams, two radioactive scintillation cocktails have to be treated. They are composed of a mix of organic liquids and water: for the first one, 19 % of organic compounds (xylene, mesitylene, diphenyloxazole, TBP...) and 86.9 % of water, and for the second one, 23 % of organic compounds (TBP...) and 77 % of water. They contain halogens (chlorine and fluorine), complexants agents (nitrate, sulphate, oxalate and formate) and have got αβγ spectra with mass activities equal to some 100 Bq/g. Therefore, tritium is also present. As a consequence, in order for storage acceptance at the ANDRA site, it is necessary to pre-treat the waste. An adequate solution seems to be a solidification process using NOCHAR polymers. Indeed, NOCHAR polymers correspond to an important variety of products applied to the treatment of radioactive aqueous and organic liquids (solvent, oil, solvent/oil mixing ...) and sludge through a mechanical and chemical solidification process. For Cadarache LOR, N910 and N960 respectively dedicated to the organic and aqueous liquids solidification are considered. With the N910, the organic waste solidification occurs in two steps. As the organic liquid travels moves through the polymer strands, the strands swell and