Related Experiment Video
Updated: Jun 14, 2025
05:03
Precise Electrochemical Sizing of Individual Electro-Inactive Particles
Published on: August 4, 2023
1.2K
Reaction Rate Theory for Electric Field Catalysis in Solution
Sohang Kundu1, Timothy C Berkelbach1,2
1Department of Chemistry, Columbia University, New York, New York 10027, United States.
Journal of the American Chemical Society
|September 5, 2024
Summary
External electric fields can control chemical reactions in solution. Our theory shows that solvent effects, including nonlinear responses, are crucial for understanding electric field catalysis, with potential for recovery at higher field strengths.
Area of Science:
- Physical Chemistry
- Chemical Reaction Dynamics
- Computational Chemistry
Background:
- External electric fields offer a novel method for manipulating chemical reactions.
- Understanding solvent effects is critical for electric field catalysis in solution.
- Previous theories often neglect solvent dynamics and nonlinear responses.
Purpose of the Study:
- To develop a transition state theory incorporating solvent effects for electric field catalysis.
- To investigate the influence of solvent polarity and dynamics on reaction rates under electric fields.
- To explore the recovery of electric field catalysis through nonlinear solvent response.
Main Methods:
- Formulation of transition state theory using a dielectric continuum model.
- Inclusion of solvent motion dynamics via Grote-Hynes corrections.
- Application to the Menshutkin reaction (CH3I + pyridine) and a symmetric SN2 reaction (F- + CH3F).
Main Results:
- Linear solvent response predicts near-complete quenching of electric field catalysis at low fields.
- Nonlinear solvent response (dielectric saturation) indicates potential catalysis recovery at higher fields.
- Dynamical corrections show non-monotonic dependence of rate constants on solvent polarity.
Conclusions:
- Solvent's linear response significantly attenuates electric field catalysis.
- Nonlinear solvent effects, like dielectric saturation, are essential for understanding catalysis at higher fields.
- Solvent dynamics and polarity play complex roles in modulating electric field effects on reaction rates.
Related Concept Videos
02:50Catalysis
26.8K
The presence of a catalyst affects the rate of a chemical reaction. A catalyst is a substance that can increase the reaction rate without being consumed during the process. A basic comprehension of a catalysts’ role during chemical reactions can be understood from the concept of reaction mechanisms and energy diagrams.
26.8K
02:53Reaction Rate
51.8K
The rate of reaction is the change in the amount of a reactant or product per unit time. Reaction rates are therefore determined by measuring the time dependence of some property that can be related to reactant or product amounts. Rates of reactions that consume or produce gaseous substances, for example, are conveniently determined by measuring changes in volume or pressure.
The mathematical representation of the change in the concentration of reactants and products, over time, is the rate...
The mathematical representation of the change in the concentration of reactants and products, over time, is the rate...
51.8K
02:28Effect of Temperature Change on Reaction Rate
4.0K
The Arrhenius equation,
4.0K
02:24Predicting Reaction Outcomes
8.3K
Kinetics describes the rate and path by which a reaction occurs. In contrast, thermodynamics deals with state functions and describes the properties, behavior, and components of a system. It is not concerned with the path taken by the process and cannot address the rate at which a reaction occurs. Although it does provide information about what can happen during a reaction process, it does not describe the detailed steps of what appears on an atomic or a molecular level. On the other hand,...
8.3K
01:13Introduction to Mechanisms of Enzyme Catalysis
8.0K
For many years, scientists thought that enzyme-substrate binding took place in a simple "lock-and-key" fashion. This model stated that the enzyme and substrate fit together perfectly in one instantaneous step. However, current research supports a more refined view scientists call induced fit. The induced-fit model expands upon the lock-and-key model by describing a more dynamic interaction between enzyme and substrate. As the enzyme and substrate come together, their interaction causes...
8.0K
03:08Rate-Determining Steps
32.1K
Relating Reaction Mechanisms
In a multistep reaction mechanism, one of the elementary steps progresses significantly slower than the others. This slowest step is called the rate-limiting step (or rate-determining step). A reaction cannot proceed faster than its slowest step, and hence, the rate-determining step limits the overall reaction rate.
The concept of rate-determining step can be understood from the analogy of a 4-lane freeway with a short-stretch of traffic-bottleneck caused due to...
In a multistep reaction mechanism, one of the elementary steps progresses significantly slower than the others. This slowest step is called the rate-limiting step (or rate-determining step). A reaction cannot proceed faster than its slowest step, and hence, the rate-determining step limits the overall reaction rate.
The concept of rate-determining step can be understood from the analogy of a 4-lane freeway with a short-stretch of traffic-bottleneck caused due to...
32.1K