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Related Concept Videos

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...
Effect of Temperature Change on Reaction Rate02:28

Effect of Temperature Change on Reaction Rate

The Arrhenius equation,
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...
Le Chatelier's Principle: Changing Temperature02:19

Le Chatelier's Principle: Changing Temperature

Consistent with the law of mass action, an equilibrium stressed by a change in concentration will shift to re-establish equilibrium without any change in the value of the equilibrium constant, K. When an equilibrium shifts in response to a temperature change, however, it is re-established with a different relative composition that exhibits a different value for the equilibrium constant.
To understand this phenomenon, consider the elementary reaction:
Entropy01:18

Entropy

The first law of thermodynamics is quantitatively formulated via an equation relating the internal energy of a system, the heat exchanged by it, and the work done on it. A quantitative formulation of the second law of thermodynamics leads to defining a state function, the entropy.
When an ideal gas expands isothermally, the disorder in the gas increases. From the molecular perspective, the gas molecules have more volume to move around in.
Consider an infinitesimal step in the expansion, which...
Acid-Catalyzed Hydration of Alkenes02:45

Acid-Catalyzed Hydration of Alkenes

Alkenes react with water in the presence of an acid to form an alcohol. In the absence of acid, hydration of alkenes does not occur at a significant rate, and the acid is not consumed in the reaction. Therefore, alkene hydration is an acid-catalyzed reaction.

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Temperature (over)compensation in an oscillatory surface reaction.

Raphael Nagao1, Irving R Epstein, Ernesto R Gonzalez

  • 1Instituto de Química de São Carlos, Universidade de São Paulo, C.P. 780, CEP 13560-970, São Carlos - SP, Brasil.

The Journal of Physical Chemistry. A
|April 25, 2008
PubMed
Summary

Temperature compensation is rare in chemical oscillators, but observed in formic acid oxidation on platinum electrodes. This study reveals complex temperature-dependent dynamics influencing biological rhythm mechanisms.

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Area of Science:

  • Electrochemistry
  • Chemical Kinetics
  • Physical Chemistry

Background:

  • Biological rhythms exhibit temperature compensation, a phenomenon rare in chemical oscillators.
  • Understanding temperature effects on chemical oscillations is crucial for diverse scientific fields.

Purpose of the Study:

  • Investigate temperature's influence on oscillatory dynamics during formic acid catalytic oxidation.
  • Explore the prevalence and characteristics of temperature compensation in this electrochemical system.

Main Methods:

  • Galvanostatic control experiments on a polycrystalline platinum electrode.
  • Measurements conducted across a temperature range of 5 to 25 °C.
  • Analysis of oscillatory period and amplitude variations with temperature and applied current.

Main Results:

  • Non-Arrhenius behavior observed under oscillatory conditions, with overcompensation (q(10) < 1) prevalent.
  • Temperature compensation (q(10) ≈ 1) observed at high applied currents.
  • Complex interplay between temperature, applied current, and distance from thermodynamic equilibrium dictates dynamics.

Conclusions:

  • The catalytic oxidation of formic acid exhibits unique temperature-dependent oscillatory behavior.
  • Non-Arrhenius dynamics arise from coupled reaction steps rather than individual step dependencies.
  • Findings offer insights into the rare phenomenon of temperature compensation in chemical systems.