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Related Concept Videos

Predicting Reaction Outcomes02:24

Predicting Reaction Outcomes

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,...
Thermochemical Equations02:55

Thermochemical Equations

For a chemical reaction (the system) carried out at constant pressure – with the only work done caused by expansion or contraction – the enthalpy of reaction (also called the heat of reaction, ΔHrxn) is equal to the heat exchanged with the surroundings (qp).
Temperature Dependence on Reaction Rate02:55

Temperature Dependence on Reaction Rate

The Collision Theory
Atoms, molecules, or ions must collide before they can react with each other. Atoms must be close together to form chemical bonds. This premise is the basis for a theory that explains many observations regarding chemical kinetics, including factors affecting reaction rates.
The collision theory is based on the postulates that (i) the reaction rate is proportional to the rate of reactant collisions, (ii) the reacting species collide in an orientation allowing contact between...
Thermal Sigmatropic Reactions: Overview01:16

Thermal Sigmatropic Reactions: Overview

Sigmatropic rearrangements are a class of pericyclic reactions in which a σ bond migrates from one part of a π system to another. These are intramolecular rearrangements where the total number of σ and π bonds remain unchanged.
Sigmatropic shifts are classified based on an order term [i, j ], where i and j indicate the number of atoms across which each end of the σ bond migrates. Below are examples of a [3,3] sigmatropic shift in 1,5-hexadiene, referred to as...
Thermodynamics: Chemical Potential and Activity01:10

Thermodynamics: Chemical Potential and Activity

The effective concentration of a species in a solution can be expressed precisely in terms of its activity. Activity considers the effect of electrolytes present in the vicinity of the species of interest and depends on the ionic strength of the solution. The activity of a species is expressed as the product of molar concentration and the activity coefficient of the species.
The thermodynamic equilibrium constant is more accurately defined in terms of activity rather than concentration.
Thermodynamic Background01:18

Thermodynamic Background

The law of mass action states that "the rate of a chemical reaction is directly proportional to the product of the molar concentrations of the reactants." It means that the more 'active mass' or 'concentration' of the reactants present, the faster the reaction will proceed.In a chemical reaction, there are forward and reverse reactions. The forward reaction is the process where the reactants combine to form products. The reverse reaction is the process where the products break down to form the...

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Updated: Jul 6, 2026

Hot Biological Catalysis: Isothermal Titration Calorimetry to Characterize Enzymatic Reactions
13:00

Hot Biological Catalysis: Isothermal Titration Calorimetry to Characterize Enzymatic Reactions

Published on: April 4, 2014

Thermochemical kinetics: does it still give insights?

Robin Walsh1

  • 1Department of Chemistry, University of Reading, Whiteknights, PO Box 224, Reading, UK RG6 6AD. r.walsh@reading.ac.uk

Chemical Society Reviews
|March 26, 2008
PubMed
Summary

This review revisits Benson

Area of Science:

  • Physical Organic Chemistry
  • Quantitative Chemistry

Background:

  • Revisiting Sidney Benson's seminal 1968 work on thermochemistry.
  • Establishing the subject's relevance in quantitative chemistry.
  • Highlighting the enduring utility of Benson's contributions.

Purpose of the Study:

  • To review the fundamental principles of Benson's work.
  • To illustrate the application of thermochemical principles in understanding reaction mechanisms.
  • To demonstrate the continued relevance of Benson's methods in modern chemical research.

Main Methods:

  • Review of established thermochemical principles and Benson's methodologies.
  • Selection of key themes to demonstrate practical applications.
  • Analysis of specific examples including strain enthalpies, chain reactions, and carbene involvement.

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Submillisecond Conformational Changes in Proteins Resolved by Photothermal Beam Deflection
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Submillisecond Conformational Changes in Proteins Resolved by Photothermal Beam Deflection

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Measuring Biomolecular DSC Profiles with Thermolabile Ligands to Rapidly Characterize Folding and Binding Interactions
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Measuring Biomolecular DSC Profiles with Thermolabile Ligands to Rapidly Characterize Folding and Binding Interactions

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Last Updated: Jul 6, 2026

Hot Biological Catalysis: Isothermal Titration Calorimetry to Characterize Enzymatic Reactions
13:00

Hot Biological Catalysis: Isothermal Titration Calorimetry to Characterize Enzymatic Reactions

Published on: April 4, 2014

Submillisecond Conformational Changes in Proteins Resolved by Photothermal Beam Deflection
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Submillisecond Conformational Changes in Proteins Resolved by Photothermal Beam Deflection

Published on: February 18, 2014

Measuring Biomolecular DSC Profiles with Thermolabile Ligands to Rapidly Characterize Folding and Binding Interactions
09:15

Measuring Biomolecular DSC Profiles with Thermolabile Ligands to Rapidly Characterize Folding and Binding Interactions

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Main Results:

  • Demonstration of the utility of thermochemical analysis in evaluating quantities.
  • Insight into the mechanisms of various chemical reactions, including those that do not readily occur.
  • Explanation of carbene involvement in hydrocarbon rearrangements using thermochemical data.

Conclusions:

  • Benson's work remains a valuable tool for quantitative chemical analysis.
  • Thermochemical principles are crucial for understanding reaction mechanisms and predicting reactivity.
  • The concepts reviewed continue to be applicable to contemporary chemical problems.