Physical Chemistry Commons^™

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.

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