scholarly journals Curly arrows, electron flow, and reaction mechanisms from the perspective of the bonding evolution theory

2017 ◽  
Vol 19 (43) ◽  
pp. 29031-29046 ◽  
Author(s):  
Juan Andrés ◽  
Patricio González-Navarrete ◽  
Vicent Sixte Safont ◽  
Bernard Silvi
Keyword(s):  
Reaction Mechanism ◽  
Reaction Mechanisms ◽  
Electron Flow ◽  
Evolution Theory ◽  
Reaction Progress ◽  
Flow Processes

The BET study provides the nature of the reaction mechanism by finding the electronic flow processes along the reaction progress.

A Paramedic Treatment for Modeling Explicitly Solvated Chemical Reaction Mechanisms

2018 ◽  
Author(s):  
Yasemin Basdogan ◽  
John Keith
Keyword(s):  
Reaction Mechanism ◽  
Chemical Reaction ◽  
Reaction Mechanisms ◽  
Reaction Pathway ◽  
Optimization Procedure ◽  
Cost Effective ◽  
Chemical Reaction Mechanisms ◽  
Solvent Molecules ◽  
Dynamics Simulations ◽  
Mbh Reaction

<div> <div> <div> <p>We report a static quantum chemistry modeling treatment to study how solvent molecules affect chemical reaction mechanisms without dynamics simulations. This modeling scheme uses a global optimization procedure to identify low energy intermediate states with different numbers of explicit solvent molecules and then the growing string method to locate sequential transition states along a reaction pathway. Testing this approach on the acid-catalyzed Morita-Baylis-Hillman (MBH) reaction in methanol, we found a reaction mechanism that is consistent with both recent experiments and computationally intensive dynamics simulations with explicit solvation. In doing so, we explain unphysical pitfalls that obfuscate computational modeling that uses microsolvated reaction intermediates. This new paramedic approach can promisingly capture essential physical chemistry of the complicated and multistep MBH reaction mechanism, and the energy profiles found with this model appear reasonably insensitive to the level of theory used for energy calculations. Thus, it should be a useful and computationally cost-effective approach for modeling solvent mediated reaction mechanisms when dynamics simulations are not possible. </p> </div> </div> </div>

Determination of Complex Reaction Mechanisms

2006 ◽  
Author(s):  
John Ross ◽  
Igor Schreiber ◽  
Marcel O. Vlad
Keyword(s):  
Reaction Mechanism ◽  
Reaction Mechanisms ◽  
Reaction Pathway ◽  
Chemical Species ◽  
Rate Coefficients ◽  
Chemical System ◽  
Evolutionary Development ◽  
Complex Reaction ◽  
Oscillatory Reactions

In a chemical system with many chemical species several questions can be asked: what species react with other species: in what temporal order: and with what results? These questions have been asked for over one hundred years about simple and complex chemical systems, and the answers constitute the macroscopic reaction mechanism. In Determination of Complex Reaction Mechanisms authors John Ross, Igor Schreiber, and Marcel Vlad present several systematic approaches for obtaining information on the causal connectivity of chemical species, on correlations of chemical species, on the reaction pathway, and on the reaction mechanism. Basic pulse theory is demonstrated and tested in an experiment on glycolysis. In a second approach, measurements on time series of concentrations are used to construct correlation functions and a theory is developed which shows that from these functions information may be inferred on the reaction pathway, the reaction mechanism, and the centers of control in that mechanism. A third approach is based on application of genetic algorithm methods to the study of the evolutionary development of a reaction mechanism, to the attainment given goals in a mechanism, and to the determination of a reaction mechanism and rate coefficients by comparison with experiment. Responses of non-linear systems to pulses or other perturbations are analyzed, and mechanisms of oscillatory reactions are presented in detail. The concluding chapters give an introduction to bioinformatics and statistical methods for determining reaction mechanisms.

scholarly journals Recent advances in understanding oxygen evolution reaction mechanisms over iridium oxide

2021 ◽  
Author(s):  
Takahiro Naito ◽  
Tatsuya Shinagawa ◽  
Takeshi Nishimoto ◽  
Kazuhiro Takanabe
Keyword(s):  
Reaction Mechanism ◽  
Oxygen Evolution ◽  
Oxygen Evolution Reaction ◽  
Reaction Mechanisms ◽  
State Of The Art ◽  
Iridium Oxide ◽  
The State ◽  
Computational Studies ◽  
Recent Advances ◽  
Iridium Oxides

Recent spectroscopic and computational studies concerning the oxygen evolution reaction over iridium oxides are reviewed to provide the state-of-the-art understanding of its reaction mechanism.

scholarly journals Experimental validation of the reaction mechanism models of dechlorination and [Zn] reclaiming in the roasting steelmaking zinc-rich dust process

2020 ◽  
Vol 39 (1) ◽  
pp. 107-116
Author(s):  
Hongyang Wang ◽  
Kai Dong ◽  
Rong Zhu
Keyword(s):  
Reaction Mechanism ◽  
Dust Particle ◽  
Chemical Reaction ◽  
Reaction Mechanisms ◽  
Experimental Validation ◽  
Step Process ◽  
Mass Percent ◽  
Mechanism Model ◽  
Air Atmosphere ◽  
Almost All

AbstractThe reaction mechanism models of dechlorination and [Zn] reclaiming in the roasting steelmaking zincrich dust process are studied. The dust collected from a steelwork contains 63.8% zinc and 3.18% chlorine (mass percent), of which, almost all zinc elements exist in ZnO and ZnCl2 forms, and all the chlorine elements are stored in ZnCl2. When the dust is roasted at above 732∘C in an air atmosphere, the ZnCl2 in the steelmaking zinc-rich dust is volatilized into steam and then oxidized into ZnO. Finding the position where the chemical reaction occurs is the key to determining the reaction mechanisms of dechlorination and [Zn] reclaiming. In this study, two groups of thermal experiments are designed and executed for roasting in different atmosphere environments and at different roasting temperatures. Based on the experiment results, the mechanism model is discussed and built, and the reaction of dechlorination and [Zn] reclaiming is shown to be a multi-step process. Because O2 from the air cannot transmit into the dust particle interior or dust bed effectively, the chemical reaction of [Zn] reclaiming occurs in the external gas environment outside of the dust, where the [Zn] recalcining reaction should be limited by the dynamics of new nucleation of ZnO solids.

scholarly journals TfOH-Promoted Reaction of 2,4-Diaryl-1,1,1-Trifluorobut-3-yn-2-oles with Arenes: Synthesis of 1,3-Diaryl-1-CF3-Indenes and Versatility of the Reaction Mechanisms

Molecules ◽  
2018 ◽  
Vol 23 (12) ◽  
pp. 3079 ◽  
Author(s):  
Aleksey V. Zerov ◽  
Anna N. Kazakova ◽  
Irina A. Boyarskaya ◽  
Taras L. Panikorovskii ◽  
Vitalii V. Suslonov ◽  
...  
Keyword(s):  
Reaction Mechanism ◽  
Reaction Mechanisms ◽  
Room Temperature ◽  
Ring Closure ◽  
Nucleophilic Attack ◽  
New Process ◽  
Intramolecular Ring ◽  
Propargyl Alcohols

The TfOH-mediated reactions of 2,4-diaryl-1,1,1-trifluorobut-3-yn-2-oles (CF3-substituted diaryl propargyl alcohols) with arenes in CH2Cl2 afford 1,3-diaryl-1-CF3-indenes in yields up to 84%. This new process for synthesis of such CF3-indenes is complete at room temperature within one hour. The synthetic potential, scope, and limitations of this reaction were illustrated by more than 70 examples. The proposed reaction mechanism invokes the formation of highly reactive CF3-propargyl cation intermediates that can be trapped at the two mesomeric positions by the intermolecular nucleophilic attack of an arene partner with a subsequent intramolecular ring closure.

scholarly journals Study of Interaction between Tigecycline and Sulbactam

2019 ◽  
pp. 1-9
Author(s):  
Hakan Sezgin Sayiner ◽  
Fatma Genç ◽  
Fatma Kandemirli
Keyword(s):  
Electronic Structure ◽  
Reaction Mechanism ◽  
Peripheral Neuropathy ◽  
Drug Interactions ◽  
Reaction Mechanisms ◽  
Bond Formation ◽  
Therapeutic Drug ◽  
Energetic Condition ◽  
Biochemical Systems ◽  
Semi Empirical

Drug interactions can have desired, reduced or unwanted effects. The probability of interactions increases with the number of drugs taken. Side effects or therapeutic drug interactions can increase or decrease the effects of one or two drugs. Failure may result from clinically meaningful interactions. Clinicians rarely use foreseeable drug-drug interactions to produce the desired therapeutic effect. For example, when we consider two drugs each causing, peripheral neuropathy increases the likelihood of neuropathy occurrence. In this study geometry optimizations of tigecycline and sulbactam drugs and their combination have been carried out with the evaluation of B3LYP/6-311G (d, p), B3LYP/6-311G (2d, 2p) levels, and the reaction mechanism at semi empirical PM6, which was parameterized for biochemical systems and B3LYP/6-311G (d,p) levels. The main objective of the study is to understand the interaction ofsulbactam with tigecycline, to describe energetic condition of bond formation and electronic structure (orders of the broken and formed bonds). The reaction mechanisms of sulbactam with tigecycline have been studied as stepwise and concerted mechanisms using semi-empircal PM6 and B3LYP/6-311G (d,p) levels.

New challenges of electrokinetic studies in investigating the reaction mechanism of electrochemical CO2 reduction

2018 ◽  
Vol 6 (29) ◽  
pp. 14043-14057 ◽  
Author(s):  
Chan Woo Lee ◽  
Nam Heon Cho ◽  
Sang Won Im ◽  
Michael Shincheon Jee ◽  
Yun Jeong Hwang ◽  
...  
Keyword(s):  
Reaction Mechanism ◽  
Reaction Mechanisms ◽  
Co2 Reduction ◽  
Electrochemical Co2 Reduction ◽  
New Challenges

New challenges for electrokinetic studies of CO2 reduction are addressed with the suggested reaction mechanisms of CO and HCOO− production.

Working with mental models to learn and visualize a new reaction mechanism

2019 ◽  
Vol 20 (3) ◽  
pp. 554-569 ◽  
Author(s):  
Amanda Bongers ◽  
Georg Northoff ◽  
Alison B. Flynn
Keyword(s):  
Reaction Mechanism ◽  
Mental Models ◽  
Reaction Mechanisms ◽  
Teaching And Learning ◽  
Conceptual Models ◽  
First Year ◽  
Molecular Processes ◽  
Chemistry Students ◽  
Epoxide Opening ◽  
Novices And Experts

Creating and using models are essential skills in chemistry. Novices and experts alike rely on conceptual models to build their own personal mental models for predicting and explaining molecular processes. There is evidence that chemistry students lack rich mental models of the molecular level; their mental models of reaction mechanisms have often been described as static and not process-oriented. Our goal in this study was to characterize the various mental models students may have when learning a new reaction mechanism and to explore how they use them in different situations. We explored the characteristics of first year organic chemistry students’ (N = 7) mental models of epoxide-opening reaction mechanisms by qualitative analysis of transcripts and written answers following an audio-recorded interview discussion. We discovered that individual learners relied on a combination of both static (with a focus on symbolism and patterns) and dynamic (reactivity as process or as particles in motion) working mental models, and that different working mental models were used depending on the task. Static working mental models were typically used to reason generally about the reaction mechanism and products that the participants provided. Dynamic working mental models were commonly used when participants were prompted to describe how they pictured the reaction happening, and in attempting to describe the structure of a transition state. Implications for research, teaching, and learning from these findings are described herein.

On the Mechanism of the Stevens Rearrangement

Synthesis ◽  
2019 ◽  
Vol 52 (01) ◽  
pp. 21-26 ◽  
Author(s):  
Daler Baidilov
Keyword(s):  
Organic Chemistry ◽  
Reaction Mechanism ◽  
Reaction Mechanisms ◽  
Computational Results ◽  
Stevens Rearrangement

The reaction mechanism for the Stevens rearrangement is one of the most controversial reaction mechanisms in organic chemistry. This account will address that controversy reviewing the experimental as well as some computational results.1 Introduction2 Evolution of the Mechanistic Knowledge2.1 Stevens (1928)2.2 Stevens (1930)2.3 Stevens (1932)2.4 Campbell (1946)2.5 Hauser (1951)2.6 Kline (1952)2.7 Lepley (1969)2.8 Baldwin (1970)3 Computational Investigations4 [2,3]-Stevens Rearrangement?5 Conclusion

Investigating first-year undergraduate chemistry students’ reasoning with reaction coordinate diagrams when choosing among particulate-level reaction mechanisms

2021 ◽  
Author(s):  
Molly B. Atkinson ◽  
Michael Croisant ◽  
Stacey Lowery Bretz
Keyword(s):  
Reaction Mechanism ◽  
Reaction Mechanisms ◽  
Peak Height ◽  
Student Thinking ◽  
Reaction Coordinate ◽  
First Year ◽  
Phase Reaction ◽  
Structured Interviews ◽  
Surface Features ◽  
Undergraduate Chemistry

Reaction coordinate diagrams (RCDs) are an important tool used to visualize the energetics of a chemical reaction. RCDs provide information about the kinetics of the reaction, the mechanism by which the reaction occurs, and the relative thermodynamic stability of the molecules in a reaction. Previous research studies have characterized student thinking about chemical kinetics, including their confusion in distinguishing between kinetics and thermodynamics. Semi-structured interviews were conducted with 44 students enrolled in a second-semester, first-year undergraduate chemistry course to elicit students’ ideas about surface features of RCDs and to examine how students connect those surface features to features of particulate-level reaction mechanisms. Students were provided both a gas-phase reaction and its accompanying RCD, and then they were asked to choose the particulate-level reaction mechanism that best corresponded to both the reaction and the RCD from among several possible particulate-level reaction mechanisms. Students were asked to explain their reasoning throughout the interview. Findings include students who chose the correct mechanism with appropriate reasoning, as well as students who chose the correct mechanism yet still expressed inaccurate ideas related to the surface features of RCDs and the concepts encoded within them. Students struggled to explain and reason with surface features such as peaks, valleys, and peak height. Moreover, students frequently found it difficult to identify meaningful connections between these surface features, the stoichiometry of the reaction, and the steps in a reaction mechanism. In addition, many students failed to mention important features of RCDs when describing their reasoning about the connections between particulate-level reaction mechanisms and RCDs. The implications for incorporating these research findings into teaching practices in first-year undergraduate chemistry contexts are discussed.

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