Simplified Purification of Acetonitrile for Electroanalytical Applications.
About: This article is published in Analytical Chemistry.The article was published on 1965-10-01. It has received 65 citations till now. The article focuses on the topics: Acetonitrile.
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TL;DR: Overpotentials for electrocatalytic hydrogen production and oxidation were determined from open circuit potentials and voltammograms of acidic or basic catalyst solutions under H2, and agreement between OCP values and potentials calculated using the Nernst equation is within 12 mV.
Abstract: Open circuit potentials were measured for acetonitrile solutions of a variety of acids and their conjugate bases under 1 atm H2. Acids examined were triethylammonium, dimethylformamidium, 2,6-dichloroanilinium, 4-cyanoanilinium, 4-bromoanilinium, and 4-anisidinium salts. These potentials, along with the pKa values of the acids, establish the value of the standard hydrogen electrode (SHE) potential in acetonitrile as −0.028(4) V vs the ferrocenium/ferrocene couple. Dimethylformamidium forms homoconjugates and other aggregates with dimethylformamide; open circuit potentials (OCPs) were used to quantify the extent of these reactions. Overpotentials for electrocatalytic hydrogen production and oxidation were determined from open circuit potentials and voltammograms of acidic or basic catalyst solutions under H2. For these solutions, agreement between OCP values and potentials calculated using the Nernst equation is within 12 mV. Use of the measured equilibrium potential allows direct comparison of catalytic s...
147 citations
TL;DR: In this article, the authors studied the electrochemical reduction of halonitrobenzenes in three solvents: dimethylformamide (DMF), acetonitrile (AN), and dimethyl sulfoxide (DMSO).
66 citations
TL;DR: Two new heterobimetallic phenylmercury(ii) dithiocarbamate complexes incorporating the ferrocenyl moiety, prepared and characterized by elemental analysis, UV-Vis, IR, (1)H and (13)C NMR spectroscopies, suggest that the delocalization of electron spin population can affect the magnitude of ΔE(p.
Abstract: Two new heterobimetallic phenylmercury(II) dithiocarbamate complexes incorporating the ferrocenyl moiety (C5H5)Fe(C5H4) (Fc), namely PhHgS2CN(CH2Fc)CH2C5H4N, (1) and PhHgS2CN(CH2Fc)CH2C4H3O, (2) have been prepared and characterized by elemental analysis, UV-Vis, IR, 1H and 13C NMR spectroscopies. The crystal structures of 1 and 2 showed a linear core at the Hg(II) centre of the molecule, bound by the sulfur atom of the dithiocarbamate ligand and carbon atom of the aromatic ring. Weak intermolecular Hg⋯S interactions form “head-to-tail” dimers in the cases of 1 and 2. The observed quasi-reversible cyclic voltammograms of the complexes have been corroborated by calculating gross natural electron population and gross natural electron spin population at each atom for the neutral as well its oxidized species obtained at density functional level (DFT) of theory, which suggests that the delocalization of electron spin population can affect the magnitude of ΔEp. The electronic absorption bands of both the complexes were assigned with the help of time dependent density functional theory (TD-DFT) calculations. The light harvesting properties of both 1 and 2 in conjunction with our previously reported compound PhHgS2CN(CH2Fc)CH2C6H5 (3) have been reported.
61 citations
TL;DR: In this article, the products of chemical and electrochemical oxidation of metallocenes, (C 5 H 5 ) 2 M (M Fe, Ru, Os), were investigated.
61 citations
TL;DR: It was realized shortly after 1940 that the slow disappearance or attenuation from leaves of these (DDT) surface deposits and effective residues from organic pesticides signified at least partial penetration into subsurface tissues.
Abstract: Prior to about 1945 it was not realized that spray and dust deposits of most organic insecticidal1 chemicals penetrated, in the field, into subsurface regions of sprayed citrus fruits, even though they were generally nonsystemic in action, as with some of the DN compounds and rotenone. Also, emphasis on “residues” (deposits) prior to this same time was on correlations with pest-control efficacy rather than on safe consumption of the treated commodity, so that initial deposits and aged deposits were most often obtained as weight of insecticide per unit areas of leaf (foliage) tissue2 rather than on and in mature fruits, as with sulfur, lime-sulfur, and lead arsenate, because insect populations were usually evaluated on leaves or twigs rather than on fruits. In connection with the field performance of DDT and other new insecticides against insects and mites in citriculture, however, it was realized shortly after 1940 that the slow disappearance or attenuation from leaves of these (DDT) surface deposits and effective residues from organic pesticides signified at least partial penetration into subsurface tissues (Gunther 1946 and Gunther et al. 1946).
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TL;DR: In this paper, the over-all dissociation constants of these acids were determined spectrophotometrically with the aid of indicator bases and conductometrally for H2SO4 and picric acid.
Abstract: : The indicators o-nitroaniline, o-nitro-pchloroaniline, and o-nitrodiphenylamine are about 50,000 times as strong in acetonitrile as in water. Perchloric acid behaves as a strong acid; other acids denoted by HA are weak. Except in extremely dilute solutions HBr, H2SO4, HNO3, and HCl dissociate yielding reversibly H(+) and AHA(-). The over-all dissociation constants of these acids were determined spectrophotometrically with the aid of indicator bases and conductometrically for H2SO4 and picric acid. By other suitable methods the stability constants, (K sub AHA(-) equal (AHA(-)/(HA) (A (-)), were evaluated. The value of K sub AHA(-) decreases from 1300 for H2SO4 to 250 for HBr, and 200 for HNO3 and HCl at 25 C. The following values pK sub HA are reported: HBr, 5.5; H2SO4, 7.25; and HNO3 and HCl, 8.9. Picric acid at concentrations smaller than 0.1 M dissociates into H(+) and Pi(-), and pK sub HPi(--) equals 8.9. The ion pair dissociation constants of tetraethylammonium bisulfate and of lithium nitrate were found to be 0.0014 and 0.00041, respectively.
159 citations
TL;DR: The use of carbon paste electrodes (carbon of graphite intimately mixed with an organic liquid) as substitutes for noble metal electrodes is described in this paper, which can be applied to routine analysis using standard techniques of anodic voltammetry.
106 citations
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