AbstractThe kinetics of interconversion between the conjugated (1,3) and nonconjugated (1,5) isomers of the cyclooctatetraene complexes (I) are studied.

Recent investigations of biphenyl and some derivatives have illustrated the absence of significant steric effects on the heterogeneous electron transfer rates. It was suggested that the two ring systems of biphenyl might act independently. Three 2,2′-diesters of biphenyl have been examined in the work presented here. The degree of steric hinderance exhibited by these materials is considerably greater than for those studied earlier. Results support the independent ring concept quite well. Not only do the electron transfer rates continue to be facile, but two reversible waves are observed for two of the three molecules. In this investigation, four solvent systems are examined so that information for a wider solvent distribution is obtained.

Chemischer InformationsdienstVolume 17, Issue 16 Physical Inorganic Chemistry ChemInform Abstract: Electrochemical Approach for the Determination of Homogeneous Redox Reaction Rate Constants Using the FT - FAM Method. M. GRZESZCZUK, M. GRZESZCZUKSearch for more papers by this authorD. E. SMITH, D. E. SMITHSearch for more papers by this author M. GRZESZCZUK, M. GRZESZCZUKSearch for more papers by this authorD. E. SMITH, D. E. SMITHSearch for more papers by this author First published: April 22, 1986 https://doi.org/10.1002/chin.198616031Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume17, Issue16April 22, 1986 RelatedInformation

The electrochemical reduction of three biphenyl halides was studied by Fourier transform faradaic admittance measurements. The results reflect competition between heterogeneous and homogeneous electron transfers and hydrogen atom abstraction in converting the halide to biphenyl. The hydrogen atom abstraction route prevails in the process when acetonitrile is the solvent and the decomposition rate of the initially formed halobiphenyl radical anions is high. The rate constant of the latter reaction for 2-bromobiphenyl in the acetonitrile system was determined to be equal to 1.5 x 104 s−1.

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTExperimental comparison of relative responses for alternating current and square wave polarography with irreversible and nearly irreversible systemsAri U. Ivaska and Donald E. SmithCite this: Anal. Chem. 1985, 57, 9, 1910–1912Publication Date (Print):August 1, 1985Publication History Published online1 May 2002Published inissue 1 August 1985https://pubs.acs.org/doi/10.1021/ac00286a025https://doi.org/10.1021/ac00286a025research-articleACS PublicationsRequest reuse permissionsArticle Views55Altmetric-Citations4LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose Get e-Alerts

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTApplication of on-line fast Fourier transform faradaic admittance measurements to deconvolution of heterogeneous charge transfer kinetic effects in anodic stripping voltammetryAri U. Ivaska and Donald E. SmithCite this: Anal. Chem. 1985, 57, 13, 2652–2655Publication Date (Print):November 1, 1985Publication History Published online1 May 2002Published inissue 1 November 1985https://pubs.acs.org/doi/10.1021/ac00290a050https://doi.org/10.1021/ac00290a050research-articleACS PublicationsRequest reuse permissionsArticle Views41Altmetric-Citations6LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose Get e-Alerts

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXT.beta.-Diketonate cobalt(3+) chelates. Stereoisomerism and electrochemical studies of complexes with two different ligandsJacob Saar, Donald E. Smith, and Michael CaisCite this: J. Am. Chem. Soc. 1985, 107, 24, 6807–6811Publication Date (Print):November 1, 1985Publication History Published online1 May 2002Published inissue 1 November 1985https://doi.org/10.1021/ja00310a010RIGHTS & PERMISSIONSArticle Views118Altmetric-Citations11LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (529 KB) Get e-Alerts Get e-Alerts

We have investigated the electrochemical reduction of tetraphenylethylene in dimethylformamide-0.10 M tetrabutylammonium tetrafluoroborate electrolyte. The array processor enhanced version of the FT-FAM instrumentation was used in these studies. Extensive measurements, including temperature and concentration dependence, were performed. Analysis of the data led to the conclusion that the observed wave represents a two-electron reduction with a very small potential separation (ΔE) between the first and second waves so that the waves overlap and only one admittance peak is observed at all frequencies. This electron transfer pair is coupled to a reversible homogeneous redox reaction (“nuance of the EE mechanism”). Other mechanisms, such as the simple EE and ECE without “nuances”, were inconsistent with one or more aspects of the data arrays obtained. The mechanism presented is the only one examined which seems consistent with all aspects of the experimental results. The estimation of thermodynamic and kinetic parameters is discussed, showing that it is possible to obtain reasonably accurate values of all relevant parameters. Three unique theoretical working curves were developed for this study. This investigation is especially illustrative of the power of the array processor enhanced FT-FAM instrumentation.

AbstractDie kinetische Untersuchung der Reduktion von (I) zu (II) ergibt die intermediäre Bildung des Anionradikals von (I), dessen Lebensdauer bestimmt wird.

ADVERTISEMENT RETURN TO ISSUEPREVReportNEXTThemodynamic and kinetic properties of the electrochemical cellDonald E. Smith Cite this: J. Chem. Educ. 1983, 60, 4, 299Publication Date (Print):April 1, 1983Publication History Received3 August 2009Published online1 April 1983Published inissue 1 April 1983https://doi.org/10.1021/ed060p299RIGHTS & PERMISSIONSArticle Views869Altmetric-Citations2LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (3 MB) Get e-Alerts Get e-Alerts

Heterogeneous electron transfer rates have been measured for biphenyl and six biphenyl derivatives. Results are reported here. Measurements were performed at both the mercury and platinum electrodes using the solvents acetonitrile and dimethylformamide. One observes facile electron transfer rates under all possible conditions. The rates show remarkably small influence, if any, to variations of steric interaction. Correlation of Marcus theory predictions of ks agrees with experimental data well at Hg and Pt, but with different assumptions, for the image field effect. Marcus theory-experiment agreement regarding solvent effect predictions is mixed. These observations are discussed and possible interpretations are suggested.

A theory-experiment comparison is made for ac cyclic voltammetry with the first-order EC mechanism. Theoretical rate laws are presented and their predictions examined. Experiments used the model electroactive species, cis-Cr(CO)2(dpm)2, [dpmbis(diphenylphosphino)mathane]. One-electron oxidation of this molecule at platinum is followed by isomerization of the cis cation to the trans cation. The rate constant for the cis-trans isomerization was measured using the fundamental harmonic reverse/forward peak height ratio, assuming a Nernstian heterogeneous charge-transfer step. Temperatures employed were 261 K (− 12°C), 273 K (0°C), and 293 K(20°C). The isomerization rate constants obtained and the assumption of Nernstian behavior produced good to excellent theory -experiment agreement for the dc, fundamental harmonic ac, and second harmonic ac cyclic voltammograms.

A method for resolution enhancement of a.c. polarograms (voltammograms) is presented. The method is based on deconvolution using fast Fourier transforms. Overlapped a.c. polarograms are mathematically narrowed and sharpened, retaining the peak position and linear proportionality of the sharpened peak height with concentration. The advantages and limitations of the method are demonstrated on simulated and experimental a.c. polarograms. The same approach is applicable to related techniques such as. differential pulse and square-wave polarography.

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTSimple electrochemical approach for determining rapid homogeneous redox reaction rate constantsTomislav Matusinovic and Donald E. SmithCite this: Inorg. Chem. 1981, 20, 9, 3121–3122Publication Date (Print):September 1, 1981Publication History Published online1 May 2002Published inissue 1 September 1981https://pubs.acs.org/doi/10.1021/ic50223a077https://doi.org/10.1021/ic50223a077research-articleACS PublicationsRequest reuse permissionsArticle Views37Altmetric-Citations2LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose Get e-Alerts

AC polarographic data are presented in which the applied dc potential scan utilizes a pulse program of the normal pulse polarographic type. AC data were obtained using the FFT faradaic admittance measurement protocol. These data indicated that the FFT-FAM procedure is applicable when the relatively short, large-amplitude pulses characterizing the normal pulse polarographic waveform are invoked as the de scan. The results also support conjecture regarding appropriate theoretical rate laws for such measurements.