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The Arrhenius equation relates the activation energy and the rate constant, k, for chemical reactions. In the Arrhenius equation, k = Ae−Ea/RT, R is the ideal gas constant, which has a value of 8.314 J/mol·K, T is the temperature on the kelvin scale, Ea is the activation energy in J/mole, e is the constant 2.7183, and A is a constant called the frequency factor, which is related to the frequency of collisions and the orientation of the reacting molecules.
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The anti-Markovnikov addition of hydrogen halides to an alkene is thermodynamically feasible only with HBr. The radical addition reaction with other hydrogen halides like HCl and HI is thermodynamically unfavorable.
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Free-energy diagrams, or reaction coordinate diagrams, are graphs showing the energy changes that occur during a chemical reaction. The reaction coordinate represented on the horizontal axis shows how far the reaction has progressed structurally. Positions along the x-axis close to the reactants have structures resembling the reactants, while positions close to the products resemble the products.  Peaks on the energy diagram represent stable structures with measurable lifetimes, while...
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SN2 Reaction: Kinetics02:14

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Kinetic Studies and Significance
In a chemical reaction, a relationship exists between the concentration of reactants and the rate at which the reaction proceeds. The study to measure this relationship is known as the kinetics of a chemical reaction. Kinetic studies are used to deduce the rate law of a chemical reaction, which provides information about the species involved during the transition state of the rate-determining step. Thus, kinetic studies help to derive the mechanism of a...
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Inductive Effects on Chemical Shift: Overview01:27

Inductive Effects on Chemical Shift: Overview

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The protons in unsubstituted alkanes are strongly shielded with chemical shifts below 1.8 ppm. Methine, methylene, and methyl protons appear at approximately 1.7, 1.2 and 0.7 ppm, while the proton signal from methane appears at 0.23 ppm. An electronegative substituent, such as chlorine, withdraws the electron density from the protons, increasing their chemical shift. Progressive substitution of the hydrogens in methane by chlorine shifts the proton signals increasingly downfield, to 3.05 ppm in...
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Nucleophilic Substitution Reactions02:34

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Historical perspective
In 1896, the German chemist Paul Walden discovered that he could interconvert pure enantiomeric (+) and (-) malic acids through a series of reactions. This conversion suggested the involvement of optical inversion during the substitution reaction. Further, in 1930, Sir Christopher Ingold described for the first time two different forms of nucleophilic substitution reactions, which are known as SN1 (nucleophilic substitution unimolecular) and SN2 (nucleophilic substitution...
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Related Experiment Video

Updated: May 23, 2025

Selective Area Modification of Silicon Surface Wettability by Pulsed UV Laser Irradiation in Liquid Environment
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The OH + CH3SH process: Potential energy surface and theoretical dynamics study.

C Rangel1, J Espinosa-Garcia2

  • 1Area de Química Orgánica, Universidad de Extremadura, 06071 Badajoz, Spain.

The Journal of Chemical Physics
|March 10, 2025
PubMed
Summary

A new potential energy surface, PES-2024, accurately models the OH + CH3SH reaction, including methyl and thiol hydrogen abstraction. Quasi-classical trajectory calculations show energy primarily deposited into water vibrational modes, matching experimental data.

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Multiscale Sampling of a Heterogeneous Water/Metal Catalyst Interface using Density Functional Theory and Force-Field Molecular Dynamics
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Area of Science:

  • Chemical Kinetics
  • Theoretical Chemistry
  • Computational Chemistry

Background:

  • The OH + CH3SH reaction is complex, featuring 18 degrees of freedom and two distinct reaction channels: methyl-H and thiol-H abstraction.
  • Intermediate complexes in both entrance and exit channels add to the reaction's complexity.
  • Accurate modeling requires a detailed potential energy surface (PES) that captures these intricate features.

Purpose of the Study:

  • To develop the first analytical full-dimensional potential energy surface (PES-2024) for the polyatomic OH + CH3SH gas-phase reaction.
  • To accurately describe both methyl- and thiol-H abstraction reaction channels.
  • To provide a reliable theoretical tool for investigating the reaction dynamics and product state distributions.

Main Methods:

  • Development of the PES-2024 within the valence bond-molecular mechanics (VB-MM) framework.
  • Utilized a reduced set of high-level ab initio calculations as input data for PES construction.
  • Performed quasi-classical trajectory (QCT) calculations at room temperature using the developed PES.

Main Results:

  • PES-2024 successfully describes both methyl- and thiol-H abstraction pathways, forming water (H2O).
  • The surface accurately represents the reaction topology, including high exothermicity, low energy barriers, and intermediate complexes.
  • QCT calculations revealed that available energy is predominantly channeled into vibrational excitations of the H2O product (44% and 47% for stretching and bending modes).

Conclusions:

  • The newly developed PES-2024 provides a robust description of the OH + CH3SH reaction dynamics.
  • The theoretical vibrational state distributions of H2O products align well with recent experimental findings.
  • PES-2024 serves as a reliable surface for future theoretical studies of this important gas-phase reaction.