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Correction to "Isokinetics".

The journal of physical chemistry. A·2019
Same author

Isokinetics.

The journal of physical chemistry. A·2019
See all related articles
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Related Experiment Video

Updated: Aug 8, 2025

A Human-machine-interface Integrating Low-cost Sensors with a Neuromuscular Electrical Stimulation System for Post-stroke Balance Rehabilitation
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A Physical Basis for Kinetic Compensation.

Richard E Lyon1

  • 1Aviation Research Division, Federal Aviation Administration W. J. Hughes Technical Center, Atlantic City International Airport, Egg Harbor Township, New Jersey 08405, United States.

The Journal of Physical Chemistry. A
|March 3, 2023
PubMed
Summary
This summary is machine-generated.

The kinetic compensation effect (KCE), a correlation between activation energy and frequency factor, may stem from reaction path dependence. This study proposes a physical basis for KCE and isokinetic relationships (IKR).

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Area of Science:

  • Physical Chemistry
  • Chemical Kinetics
  • Thermodynamics

Background:

  • The kinetic compensation effect (KCE) describes a positive correlation between Arrhenius activation energy (E) and frequency factor (A).
  • Despite over 100 years of research and thousands of publications, the cause of KCE remains debated.
  • KCE is often visualized using Constable plots, showing a linear relationship between ln[A] and E/R.

Purpose of the Study:

  • To propose a physical basis for the kinetic compensation effect (KCE) and isokinetic relationship (IKR).
  • To suggest that KCE arises from the path dependence of reaction history.
  • To reconcile KCE with IKR through a proposed model.

Main Methods:

  • Analysis of the single-step rate law approximation for reversible reactions.
  • Introduction of a dynamic thermal equilibrium temperature (T0 = H°/ΔS°).
  • Relating the slope of Constable/KCE plots to T0 and reaction path dependence constant (k0).

Main Results:

  • A linear relationship between ln[A] and E is attributed to path dependence of reaction history.
  • The proposed model provides a physical basis for KCE and IKR, defining a crossover temperature (1/T0).
  • Qualitative agreement was found between calculated ΔH° and ΔS° values and literature data for thermal decomposition reactions.

Conclusions:

  • The study suggests reaction path dependence as the underlying cause of the kinetic compensation effect.
  • The proposed physical model successfully reconciles KCE with isokinetic relationships.
  • The findings are supported by experimental data from thermal decomposition of organic peroxides, calcium carbonate, and poly(methyl methacrylate).