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...

Direct determination of equilibrium potentials for hydrogen oxidation/production by open circuit potential measurements in acetonitrile.

Mechanistic studies of the decomposition of halonitrobenzene anion radicals

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.

Efficient phenylmercury(II) methylferrocenyldithiocarbamate functionalized dye-sensitized solar cells

Chemical and electrochemical oxidation of metallocenes, reactions of metallocenes with mercury salts

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).

Insecticide residues in California citrus fruits and products.

Simplified Purification of Acetonitrile for Electroanalytical Applications.

A large pharmaceutical manufacturer operates an expanded pharmaceutical production facility located on the island of Puerto Rico. Waste discharge from the production facility includes pharmaceutical process waste waters, clean-up, and sanitary wastes. These wastewaters are treated and reused within the production facility or discharged into a small receiving stream under a very stringent effluent discharge limitation requiring tertiary treatment to meet organics, metals, and phosphorus requirements. Reuse currently includes cooling tower make-up and sand/carbon filter backwash; however, the wastewater treatment system design provides for complete water reuse including quench tower and flame oxidizer make-ups. 

J. W. Olver

Papers

Simplified Purification of Acetonitrile for Electroanalytical Applications.

Treatment and Reuse of Pharmaceutical Process Water