Physical Chemistry Commons^™

Some Features Of The Concentration Oscillations In The Phenylacetylene Oxidative Carbonylation Reaction (In Russian), Sergey N. Gorodsky

Sergey N. Gorodsky

Some modes of concentration oscillations in the homogeneous system KI-PdI2-CO-O2-CH3OH are described in this paper.

Energetyka Niskoemisyjna, Wojciech M. Budzianowski

Wojciech Budzianowski

No abstract provided.

Particulate Pictures And Kinetic-Molecular Theory Concepts: Seizing An Opportunity, Mark Waner

Mark J. Waner

This work examines commonly used particulate-level pictures meant to illustrate gases. These pictures are found throughout textbooks in the middle grades through the college level, as well as in questions frequently used to assess conceptual learning in students. This work uses the kinetic-molecular theory of gases to demonstrate the inaccuracies often present in these figures, which offers the opportunity to address model limitations to students and to develop better pictures. A basis for using these pictures to discuss models and ideas for ways these pictures can be used for inquiry activities based on analysis of scales is also discussed.

Kinetic And Mechanistic Studies Of The Deuterium Exchange In Classical Keto−Enol Tautomeric Equilibrium Reactions, Michael Nichols, Mark Waner

Mark J. Waner

An extension of the classic keto−enol tautomerization of β-dicarbonyl compounds into a kinetic analysis of deuterium exchange is presented. It is shown that acetylacetone and ethyl acetoacetate undergo nearly complete deuterium exchange of the α-methylene carbon when dissolved in methanol-d4. The extent of deuteration may be monitored via NMR spectroscopy as a function of time. A mechanism for deuterium exchange is presented and shown to be consistent with a consecutive first-order process. The data for acetylacetone are consistent with steady-state kinetics, whereas those of ethyl acetoacetate illustrate nonsteady-state behavior, offering an accessible example where students might collect and analyze real …

Absolute Ground-State Nitrogen Atom Density In A N2/Ch4 Late Afterglow: Talif Experiments And Modelling Studies, Et. Es-Sebbar, M.-C. Gazeau, Y. Benilan, A. Jolly, C D. Pintassilgo

Dr. Et-touhami Es-sebbar

Following a first study on a late afterglow in flowing pure nitrogen post discharge, we report new two-photon absorption laser-induced fluorescence (TALIF) measurements of the absolute ground-state atomic nitrogen density N(4S) and investigate the influence of methane introduced downstream from the discharge by varying the CH4 mixing ratio from 0% up to 50%. The N (4S) maximum density is about 2.2 × 1015 cm−3 in pure N2 for a residence time of 22 ms and does not change significantly for methane mixing ratio up to ~15%, while above, a drastic decrease is observed. The influence of the residence time has …

Experimental And Theoretical Studies On Nitrogen Plasma And Methane Photolysis: Implications For Laboratory Simulations Of Titan’S Atmosphere, M-C. Gazeau, Y. Benilan, E. Arzoumanian, Et. Es-Sebbar, A. Jolly

Dr. Et-touhami Es-sebbar

No abstract provided.

Spectroscopic Studies Applied To Uvis Observations Of Titan, Y. Benilan, F. Capalbo, Et. Es-Sebbar, N. Fray, A. Jolly, M-C. Gazeau, J-C. Guillemin, M. Schwell

Dr. Et-touhami Es-sebbar

No abstract provided.

Talif Investigation And Modelling Of The Absolute N(4s) Density In A N2-Ch4 Late Afterglow, C.D. Pintassilgo, Et. Es-Sebbar, Y. Benilan, M-C. Gazeau, A. Jolly

Dr. Et-touhami Es-sebbar

The purpose of the present work is the experimental and numerical study of the absolute ground-state nitrogen atoms density N(4S) in the late afterglow of a pure N2 flowing microwave discharge in which different amounts of CH4 have been injected at 25 cm downstream from the nitrogen discharge. The absolute N(4S) concentrations have been measured using Two-photon Absorption Laser-Induced Fluorescence (TALIF), while a detailed kinetic model has been developed to simulate both the discharge and the post-discharge regions. Theoretical predictions are then compared to experimental measurements.

Combined Experimental And Theoretical Studies On Methane Photolysis At 121.6 Nm And 248 Nm- Implications On A Program Of Laboratory Simulations Of Titan’S Atmosphere, C. Romanzin, E. Arzoumanian, Et. Es-Sebbar, A. Jolly, S. Perrier, M.-C. Gazeau, Y. Bénilan

Dr. Et-touhami Es-sebbar

Methane is, together with N2, the main precursor of Titan’s atmospheric chemistry. In our laboratory, we are currently developing a program of laboratory simulations of Titan’s atmosphere, where methane is intended to be dissociated by multiphotonic photolysis at 248 nm. A preliminary study has shown that multiphotonic absorption of methane at 248 nm is efficient and leads to the production of hydrocarbons such as C2H2 (Romanzin et al., 2008). Yet, at this wavelength, little is known about the branching ratios of the hydrocarbon radicals (CH3, CH2 and CH) and their following photochemistry. This paper thus aims at investigating methane photochemistry …

Temperature-Dependent Photoabsorption Cross-Section Of Cyano-Diacetylene In The Vacuum Uv, N. Fray, Y. Bénilan, M.-C. Gazeau, A. Jolly, M. Schwell, E. Arzoumanian, Et. Es-Sebbar, T. Ferradaz, J.- C. Guillemin

Dr. Et-touhami Es-sebbar

Using synchrotron radiation as a tunable VUV light source, we have measured, for the first time, the absolute photoabsorption cross sections of HC5N with a spectral resolution of 0.05 nm in the region between 80 and 205 nm from 233 to 298 K. The measured cross sections are used to predict the HC5N photodestruction rate in the solar system and to model a transmission spectrum in Titan's atmosphere. Comparing the latter with that acquired by the Ultraviolet Imaging Spectrograph on board the Cassini spacecraft, we have determined an upper limit of 2.7 × 10−5 on the HC5N abundance at 1100 …

Phase Transition Enthalpy Measurements Of Organic And Organometallic Compounds. Sublimation, Vaporization And Fusion Enthalpies From 1880 To 2010, William E. Acree, James S. Chickos

James Chickos

No abstract provided.

Improvement Of The Stoichiometric Network Analysis For Determination Of Instability Conditions Of Complex Nonlinear Reaction Systems, Zeljko D. Cupic

Zeljko D Cupic

No abstract provided.

2-(3-Nitrophenoxy)Quinoxaline, Hairul Anuar Bin Tajuddin

Hairul Anuar Bin Tajuddin

In the title molecule, C(14)H(9)N(3)O(3), the dihedral angle between the quinoxaline and benzene rings is 77.13 (9)degrees. The molecule is twisted about the ether-benzene O-C bond, with a C-O-C-C torsion angle of -102.8 (2)degrees. In the crystal, molecules are linked by C-H center dot center dot center dot O hydrogen bonds, forming layers in the ab plane, with one nitro O atom accepting two such interactions. The layers stack along the c-axis direction via weak C-H center dot center dot center dot pi interactions.

Grafika Inżynierska Ćw., Wojciech M. Budzianowski

Wojciech Budzianowski

No abstract provided.

Projektowanie Procesów Biotechnologicznych Proj., Wojciech M. Budzianowski

Wojciech Budzianowski

No abstract provided.

Projektowanie I Optymalizacja Procesów Proj., Wojciech M. Budzianowski

Wojciech Budzianowski

No abstract provided.

Metody Numeryczne Lab., Wojciech M. Budzianowski

Wojciech Budzianowski

No abstract provided.

Odnawialne Źródła Energii W., Wojciech M. Budzianowski

Wojciech Budzianowski

No abstract provided.

Vinyl Cations Substituted With Β Π-Donors Have Triplet Ground States, Arthur Winter, Daniel E. Falvey

Arthur Winter

Computations at the CASPT2, CBS-QB3, and B3LYP levels of theory demonstrate that β-substitution of vinyl cations with π-donors switches the ground state of these ions from the familiar closed-shell singlet state to a carbene-like triplet state similar to the electronic state of triplet phenyl cations. Although the parent vinyl cation is a ground-state singlet species with a very large energy gap to the lowest energy triplet state, substituting the β hydrogens with just one strong π-donor (e.g., NH2, NMe2, OMe) or two moderate π-donors (e.g., F, OH, Ar, vinyl) makes the triplet state the computed ground electronic state. In many …

Size Effect Of Ruthenium Nanoparticles In Catalytic Carbon Monoxide Oxidation, Sang Hoon Joo, Jeong Y. Park, J. Russell Renzas, Derek R. Butcher, Wenyu Huang, Gabor A. Somorjai

Wenyu Huang

Carbon monoxide oxidation over ruthenium catalysts has shown an unusual catalytic behavior. Here we report a particle size effect on CO oxidation over Ru nanoparticle (NP) catalysts. Uniform Ru NPs with a tunable particle size from 2 to 6 nm were synthesized by a polyol reduction of Ru(acac)3 precursor in the presence of poly(vinylpyrrolidone) stabilizer. The measurement of catalytic activity of CO oxidation over two-dimensional Ru NPs arrays under oxidizing reaction conditions (40 Torr CO and 100 Torr O2) showed an activity dependence on the Ru NP size. The CO oxidation activity increases with NP size, and the 6 nm …

Highly Active Heterogeneous Palladium Nanoparticle Catalysts For Homogeneous Electrophilic Reactions In Solution And The Utilization Of A Continuous Flow Reactor, Wenyu Huang, Jack Hung Chang Liu, Pinar Alayoglu, Yimin Li, Cole A. Whitman, Chia-Kuang Tsung, F. Dean Toste, Gabor A/ Somorjai

Wenyu Huang

highly active heterogeneous Pd-nanoparticle catalyst for the intramolecular addition of phenols to alkynes was developed and employed in a continuous flow reaction system. Running the reaction in flow mode revealed reaction kinetics, such as the activation energy and catalyst deactivation, and provides many potential practical advantages.

Seedless Polyol Synthesis And Co Oxidation Activity Of Monodisperse (111)- And (100)-Oriented Rhodium Nanocrystals In Sub-10 Nm Sizes, Yawen Zhang, Michael E. Grass, Wenyu Huang, Gabor A. Somoraji

Wenyu Huang

Monodisperse sub-10 nm (6.5 nm) sized Rh nanocrystals with (111) and (100) surface structures were synthesized by a seedless polyol reduction in ethylene glycol, with poly(vinylpyrrolidone) as a capping ligand. When using [Rh(Ac)2]2 as the metal precursor, (111)-oriented Rh nanopolyhedra containing 76% (111)-twinned hexagons (in 2D projection) were obtained; whereas, when employing RhCl3 as the metal precursor in the presence of alkylammonium bromide, such as tetramethylammonium bromide and trimethyl(tetradecyl)ammonium bromide, (100)-oriented Rh nanocubes were obtained with 85% selectivity. The {100} faces of the Rh nanocrystals are stabilized by chemically adsorbed Br− ions from alkylammonium bromides, which led to (100)-oriented nanocubes. …

Furan Hydrogenation Over Pt(111) And Pt(100) Single-Crystal Surfaces And Pt Nanoparticles From 1 To 7 Nm: A Kinetic And Sum Frequency Generation Vibrational Spectroscopy Study, Christopher J. Kliewer, Cesar Aliaga, Marco Bieri, Wenyu Huang, Chia-Kuang Tsung, Jennifer B. Wood, Kyriankos Komvopoulos, Gabor A. Somorjai

Wenyu Huang

Sum frequency generation surface vibrational spectroscopy and kinetic measurements using gas chromatography have been used to systematically study the adsorption and hydrogenation of furan over Pt(111) and Pt(100) single-crystal surfaces and size-controlled 1.0-nm, 3.5-nm and 7.0-nm Pt nanoparticles at Torr pressures (10 Torr of furan, 100 Torr of H2) to form dihydrofuran, tetrahydrofuran, and the ring-cracking products butanol and propylene. As determined by SFG, the furan ring lies parallel to all Pt surfaces studied under hydrogenation conditions. Upright THF and the oxametallacycle intermediate are observed over the nanoparticle catalysts under reaction conditions. Butoxy increases in surface concentration over Pt(111) with …

The Effect Of Ion-Pairing On The Open Circuit Potential Of 3-Mercaptoproprionic Acid Modified Gold Electrodes, Mark Anderson, Alice Harper

Mark R. Anderson

Open circuit potential (OCP) measurement is used to monitor the charge of a monolayer of 3-mercaptopropionic acid. OCP is determined by the concentrations of the reduced and oxidized forms of a redox couple in the solution adjacent to the modified interface. OCP values were monitored in the presence of the one-electron redox couple Fe(CN)63-/4- as a function of solution pH. The OCP measured at basic pHs was different from the acidic OCP due to differences in electrostatic interactions between the interface and the redox species as described by the Nernst equation. The influence of ion-pairing with the monolayer is studied …

Kinetic And Mechanistic Studies Of The Deuterium Exchange In Classical Keto−Enol Tautomeric Equilibrium Reactions, Mark Waner, Michael Nichols

Mark J. Waner

An extension of the classic keto−enol tautomerization of β-dicarbonyl compounds into a kinetic analysis of deuterium exchange is presented. It is shown that acetylacetone and ethyl acetoacetate undergo nearly complete deuterium exchange of the α-methylene carbon when dissolved in methanol-d4. The extent of deuteration may be monitored via NMR spectroscopy as a function of time. A mechanism for deuterium exchange is presented and shown to be consistent with a consecutive first-order process. The data for acetylacetone are consistent with steady-state kinetics, whereas those of ethyl acetoacetate illustrate nonsteady-state behavior, offering an accessible example where students might collect and analyze real …

Cyclohexane Oxidation And Cyclohexyl Hydroperoxide Decomposition By Poly(4-Vinylpyridine-Co-Divinylbenzene) Supported Cobalt And Chromium Complexes, Zeljko D. Cupic

Zeljko D Cupic

No abstract provided.

Interdependence Of In-Cell Xenon Density And Temperature During Rb/129xe Spin-Exchange Optical Pumping Using Vhg-Narrowed Laser Diode Arrays, Nicholas Whiting, Panayiotis Nikolaou, Neil A. Eschmann, Michael J. Barlow, Boyd M. Goodson

Nicholas Whiting