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Articles 1 - 8 of 8
Full-Text Articles in Thermodynamics
Metathesis Or Isomerization: Counteranion Directed Reactivity Of Grubbs I, Paul D. Miller, Joe B. Calkins, Craig A. Bayse, Trandon A. Bender
Metathesis Or Isomerization: Counteranion Directed Reactivity Of Grubbs I, Paul D. Miller, Joe B. Calkins, Craig A. Bayse, Trandon A. Bender
Chemistry & Biochemistry Faculty Publications
Catalytic isomerization of alkenes has garnered interest for many years, but there are remaining challenges when it comes to thermodynamic selectivity and uncontrolled isomerization. Nonbiased substrates, be it sterically or thermodynamically, remain challenging for many catalysts, with a few examples available in the more modern literature. Herein, we present the controlled isomerization of linear alkenes with a cocatalytic mixture of commercially available catalyst and reagents: Grubbs I, tris(pentafluorophenyl)borane, and triethylsilane. DFT calculations indicate that an observed alkylidyne hydride intermediate is in rapid equilibrium with an alkylidene that binds the alkene substrate. This combination results in a pi-acidic metal and a …
Type-B Energetic Processes: Introduction And Invitation To Special Issue Of Energies, James Weifu Lee, Daniel P. Sheehan
Type-B Energetic Processes: Introduction And Invitation To Special Issue Of Energies, James Weifu Lee, Daniel P. Sheehan
Chemistry & Biochemistry Faculty Publications
[First paragraph] Currently, there is substantial scientific evidence for the existence of Type-B energetic processes on Earth, such as the naturally occurring transmembrane-electrostatically localized protons (TELP) thermotrophic properties in life [1]. A number of groundbreaking human-made Type-B energetic processes, including (but not limited to) “asymmetric function-gated isothermal electricity production” [2], “epicatalysis generating a temperature difference between catalysis-asymmetric filaments” [3], “artificially made asymmetric membrane concentration cell” [4,5], “Fu’s experiment on heat–electric conversion using surface electron emission under a static magnetic field” [6], and the “dynamic processes in superconductors indicating Type-B energetic process” [7,8,9] have been invented and/or experimentally demonstrated. The innovative …
Type-B Energetic Processes: Their Identification And Implications, James Weifu Lee
Type-B Energetic Processes: Their Identification And Implications, James Weifu Lee
Chemistry & Biochemistry Faculty Publications
We have now identified two thermodynamically distinct types (A and B) of energetic processes naturally occurring on Earth. Type-A energy processes, such as classical heat engines, apparently well follow the second law of thermodynamics; Type-B energy processes, such as the newly discovered thermotrophic function that isothermally utilizes environmental heat energy to perform useful work in driving ATP synthesis, follow the first law of thermodynamics (conservation of mass and energy) but do not have to be constrained by the second law, owing to their special asymmetric functions. Several Type-B energy processes such as asymmetric function-gated isothermal electricity production and epicatalysis have …
Outstanding Advantages, Current Drawbacks, And Significant Recent Developments In Mechanochemistry: A Perspective View, Silvina Pagola
Outstanding Advantages, Current Drawbacks, And Significant Recent Developments In Mechanochemistry: A Perspective View, Silvina Pagola
Chemistry & Biochemistry Faculty Publications
Although known since antiquity, mechanochemistry has remained dormant for centuries. Nowadays, mechanochemistry is a flourishing research field at the simultaneous stages of gathering data and (often astonishing) observations, and scientific argumentation toward their analysis, for which the combination of interdisciplinary expertise is necessary. Mechanochemistry’s implementation as a synthetic method is constantly increasing, although it remains far from being fully exploited, or understood on the basis of fundamental principles. This review starts by describing many remarkable advantages of mechanochemical reactions, simplifying and “greening” chemistry in solutions. This description is followed by an overview of the current main weaknesses to be addressed …
More On The Demons Of Thermodynamics, Daniel P. Sheehan, Garret Moddel, James W. Lee
More On The Demons Of Thermodynamics, Daniel P. Sheehan, Garret Moddel, James W. Lee
Chemistry & Biochemistry Faculty Publications
No abstract provided.
A Local Mode Study Of Ring Puckering Effects In The Infrared Spectra Of Cyclopentane, Edwin L. Sibert Iii, Peter F. Bernath
A Local Mode Study Of Ring Puckering Effects In The Infrared Spectra Of Cyclopentane, Edwin L. Sibert Iii, Peter F. Bernath
Chemistry & Biochemistry Faculty Publications
We report and interpret recently recorded high-resolution infrared spectra for the fundamentals of the CH2 scissors and CH stretches of gas phase cyclopentane at −26.1 and −50 ○C, respectively. We extend previous theoretical studies of this molecule, which is known to undergo barrierless pseudorotation due to ring puckering, by constructing local mode Hamiltonians of the stretching and scissor vibrations for which the frequencies, couplings, and linear dipoles are calculated as functions of the pseudorotation angle using B3LYP/6-311++(d,p) and MP2/cc-pVTZ levels of theory. Symmetrization (D5h) of the vibrational basis sets leads to simple vibration/pseudorotation Hamiltonians whose solutions …
Type-B Energetic Processes And Their Associated Scientific Implications, James Weifu Lee
Type-B Energetic Processes And Their Associated Scientific Implications, James Weifu Lee
Chemistry & Biochemistry Faculty Publications
Recently, our work has identified two thermodynamically distinct types (A and B) of energetic processes naturally occurring on Earth. Type-A energy processes such as the classical heat engines, ATP hydrolysis, and many of the known chemical, electrical, and mechanical processes apparently follow well the second law of thermodynamics; Type-B energy processes, for example, the newly discovered thermotropic function that isothermally utilizes environmental heat energy to do useful work in driving ATP synthesis, follow the first law of thermodynamics (conservation of mass and energy) but do not have to be constrained by the second law, owing to its special asymmetric functions. …
Fourier Transform Emission Spectroscopy Of Yh And Yd: Observation Of New A¹Δ And B¹Π Electronic States, R. S. Ram, G. Li, P. F. Bernath
Fourier Transform Emission Spectroscopy Of Yh And Yd: Observation Of New A¹Δ And B¹Π Electronic States, R. S. Ram, G. Li, P. F. Bernath
Chemistry & Biochemistry Faculty Publications
The emission spectra of YH and YD molecules have been investigated in the 3600–12 000 cm−1 region using a Fourier transform spectrometer. Molecules were formed in an yttrium hollow cathode lamp operated with a continuous flow of a mixture of Ne and Ar gases, and YH and YD were observed together in the same spectra. A group of bands observed near 1 μm have been identified as 0-0 and 1-1 bands of the A1Δ-X1Σ+ and B1Π-X1Σ+ transitions of YH and the 0-0 bands of the same two transitions …