A DFT investigation of the blue bottle experiment:  E ∘ half-cell  analysis of autoxidation catalysed by redox indicators

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Abstract

The blue bottle experiment is a collective term for autoxidation reactions catalysed by redox indicators. The reactions are characterized by their repeatable cycle of colour changes when shaken/left to stand and intricate chemical pattern formation. The blue bottle experiment is studied based on calculated solution-phase half-cell reduction potential of related reactions. Our investigation confirms that the reaction in various versions of the blue bottle experiment published to date is mainly the oxidation of an acyloin to a 1,2-dicarbonyl structure. In the light of the calculations, we also propose new non-acyloin reducing agents for the experiment. These results can help guide future experimental studies on the blue bottle experiment.

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Most cited references 58

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Calculation of solvation free energies of charged solutes using mixed cluster/continuum models.

Vyacheslav Bryantsev, William Iii, Mamadou Diallo (2008)

We derive a consistent approach for predicting the solvation free energies of charged solutes in the presence of implicit and explicit solvents. We find that some published methodologies make systematic errors in the computed free energies because of the incorrect accounting of the standard state corrections for water molecules or water clusters present in the thermodynamic cycle. This problem can be avoided by using the same standard state for each species involved in the reaction under consideration. We analyze two different thermodynamic cycles for calculating the solvation free energies of ionic solutes: (1) the cluster cycle with an n water cluster as a reagent and (2) the monomer cycle with n distinct water molecules as reagents. The use of the cluster cycle gives solvation free energies that are in excellent agreement with the experimental values obtained from studies of ion-water clusters. The mean absolute errors are 0.8 kcal/mol for H(+) and 2.0 kcal/mol for Cu(2+). Conversely, calculations using the monomer cycle lead to mean absolute errors that are >10 kcal/mol for H(+) and >30 kcal/mol for Cu(2+). The presence of hydrogen-bonded clusters of similar size on the left- and right-hand sides of the reaction cycle results in the cancellation of the systematic errors in the calculated free energies. Using the cluster cycle with 1 solvation shell leads to errors of 5 kcal/mol for H(+) (6 waters) and 27 kcal/mol for Cu(2+) (6 waters), whereas using 2 solvation shells leads to accuracies of 2 kcal/mol for Cu(2+) (18 waters) and 1 kcal/mol for H(+) (10 waters).

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Single-ion solvation free energies and the normal hydrogen electrode potential in methanol, acetonitrile, and dimethyl sulfoxide.

Casey P Kelly, Christopher J. Cramer, Donald G Truhlar (2007)

The division of thermodynamic solvation free energies of electrolytes into contributions from individual ionic constituents is conventionally accomplished by using the single-ion solvation free energy of one reference ion, conventionally the proton, to set the single-ion scales. Thus, the determination of the free energy of solvation of the proton in various solvents is a fundamental issue of central importance in solution chemistry. In the present article, relative solvation free energies of ions and ion-solvent clusters in methanol, acetonitrile, and dimethyl sulfoxide (DMSO) have been determined using a combination of experimental and theoretical gas-phase free energies of formation, solution-phase reduction potentials and acid dissociation constants, and gas-phase clustering free energies. Applying the cluster pair approximation to differences between these relative solvation free energies leads to values of -263.5, -260.2, and -273.3 kcal/mol for the absolute solvation free energy of the proton in methanol, acetonitrile, and DMSO, respectively. The final absolute proton solvation free energies are used to assign absolute values for the normal hydrogen electrode potential and the solvation free energies of other single ions in the solvents mentioned above.

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Comment on the Correct Use of Continuum Solvent Models

Michelle Coote, Junming Ho, Andreas Klamt (2010)

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Author and article information

Journal

Journal ID (nlm-ta): R Soc Open Sci

Journal ID (iso-abbrev): R Soc Open Sci

Journal ID (publisher-id): RSOS

Journal ID (hwp): royopensci

Title: Royal Society Open Science

Publisher: The Royal Society Publishing

ISSN (Electronic): 2054-5703

Publication date Collection: November 2017

Publication date (Electronic): 8 November 2017

Publication date PMC-release: 8 November 2017

Volume: 4

Issue: 11

Electronic Location Identifier: 170708

Affiliations

[1 ]Science Division, Mahidol University International College, Mahidol University , Salaya, Nakhon Pathom 73170, Thailand

[2 ]National Nanotechnology Center (NANOTEC), National Science and Technology Development Agency , Khlong Luang, Pathum Thani 12120, Thailand

[3 ]Department of Chemical Engineering, McGill University , Quebec H3A 0C5, Canada

Author notes

Author for correspondence: Taweetham Limpanuparb e-mail: taweetham.lim@ 123456mahidol.edu

Electronic supplementary material is available online at https://dx.doi.org/10.6084/m9.figshare.c.3918658.

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Taweetham Limpanuparb http://orcid.org/0000-0002-8558-6199

Article

Publisher ID: rsos170708

DOI: 10.1098/rsos.170708

PMC ID: 5717635

PubMed ID: 29291061

SO-VID: caeb7714-c7d3-4dde-bf7d-4fa0833decb3

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Published by the Royal Society under the terms of the Creative Commons Attribution License http://creativecommons.org/licenses/by/4.0/, which permits unrestricted use, provided the original author and source are credited.

History

Date received : 10 July 2017

Date accepted : 5 September 2017

Funding

Funded by: Institute for the Promotion of Teaching Science and Technology;

Award ID: 08/2557

Funded by: Mahidol University International College;

Award ID: 001/2016

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cover-date November, 2017

Keywords: blue bottle experiment,reduction potential,density functional theory,chemical pattern formation,reaction mechanism

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Keywords: blue bottle experiment, reduction potential, density functional theory, chemical pattern formation, reaction mechanism

A DFT investigation of the blue bottle experiment: E ^∘ _half-cell analysis of autoxidation catalysed by redox indicators

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Redox Experimental Medicine

Most cited references 58

Calculation of solvation free energies of charged solutes using mixed cluster/continuum models.

Single-ion solvation free energies and the normal hydrogen electrode potential in methanol, acetonitrile, and dimethyl sulfoxide.

Comment on the Correct Use of Continuum Solvent Models

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