Molecular dynamics investigation of ferrous-ferric electron transfer in a hydrolyzing aqueous solution: calculation of the pH dependence of the diabatic transfer barrier and the potential of mean force

We present a molecular model for ferrous-ferric electron transfer in an aqueous solution that accounts for electronic polarizability and exhibits spontaneous cation hydrolysis. An extended Lagrangian technique is introduced for carrying out calculations of electron-transfer barriers in polarizable systems. The model predicts that the diabatic barrier to electron transfer increases with increasing pH, due to stabilization of the Fe3+ by fluctuations in the number of hydroxide ions in its first coordination sphere, in much the same way as the barrier would increase with increasing dielectric constant in the Marcus theory. We have also calculated the effect of pH on the potential of mean force between two hydrolyzing ions in aqueous solution. As expected, increasing pH reduces the potential of mean force between the ferrous and ferric ions in the model system. The magnitudes of the predicted increase in diabatic transfer barrier and the predicted decrease in the potential of mean force nearly cancel each other at the canonical transfer distance of 0.55 nm. Even though hydrolysis is allowed in our calculations, the distribution of reorganization energies has only one maximum and is Gaussian to an excellent approximation, giving a harmonic free energy surface in the reorganization energy F(DeltaE) with a single minimum. There is thus a surprising amount of overlap in electron-transfer reorganization energies for Fe(2+)-Fe(H2O)6(3+), Fe(2+)-Fe(OH)(H2O)5(2+), and Fe(2+)-Fe(OH)2(H2O)+ couples, indicating that fluctuations in hydrolysis state can be viewed on a continuum with other solvent contributions to the reorganization energy. There appears to be little justification for thinking of the transfer rate as arising from the contributions of different hydrolysis states. Electronic structure calculations indicate that Fe(H2O)6(2+)-Fe(OH)n(H2O)(6-n)(3-n)+ complexes interacting through H3O2- bridges do not have large electronic couplings.     

Dialkyldithiocarbamate als Reagentien zur gas-chromatographischen Bestimmung von Metallen

Zusammenfassung Kleine Mengen Ni, Cu und Zn in wäßrigen Lösungen können nach Ausschütteln ihrer Dipropyldithiocarbamatochelate gas-chromatographisch bestimmt werden. Arbeitsbedingungen für den 0,01–1 ppm-Bereich werden angegeben. Die Reproduzierbarkeit der Bestimmung wird durch Zusatz eines inneren Standards verbessert.

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Dialkyldithiocarbamates as reagents for the gas-chromatographic determination of metalsII. Determination of zinc, copper and nickel as dipropyldithiocarbamato chelates after extraction from aqueous solution

Summary Small amounts of Ni, Cu and Zn in aqueous solutions can be determined by gas chromatography after extraction of their dipropyldithiocarbamatochelates. Working details for the 0.01–1 ppm range are reported. Reproducibility is markedly improved by addition of an inner standard.

Die Untersuchungen wurden in dankenswerter Weise durch Mittel der Deutschen Forschungsgemeinschaft und des Verbands der chemischen Industrie unterstützt.     

Transannular reactions of two parallel 1,3-butadiynes: syntheses,structures, and reactions of 1-azacyclotetradeca-3,5,10,12-tetrayne derivatives

The synthesis of 1-alkyl and 1-aryl-1-azacyclotetradeca-3,5,10,12-tetraynes was achieved in a stepwise approach. The key intermediate was 1,13-dibromotrideca-2,4,9,11-tetrayne (18). Reaction with methyl- (19 a), ethyl- (19 b), isopropyl- (19 c), n-butyl- (19 d), and tert-butylamine (19 e) as well as aniline (19 f) and p-methoxyaniline (19 g) gave the corresponding 14-membered tetraynes 20 a-20 g. The ring inversion process of 20 b was studied by variable temperature (1)H NMR spectroscopy. From these measurements a value of 10.6 kcal mol(-1) was calculated for DeltaG(not equal). X-ray investigations on single crystals of 20 b, 20 c, and 20 f revealed the axial position for the substituent at each nitrogen atom. For 20 b we encountered the chair conformation, for 20 c both chair and boat conformations, and for 20 f the boat conformation in the solid state. The reaction of 20 c with concentrated HCl in ethanol yielded 2,10-dichloro-6-isopropyl-6-azatricyclo[9.3.0.0(4,8)]tetradeca-1(11),2,4(8),9-tetraene (25 c). Compound 25 c was oxidized by 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) to 27 c. The structure of the latter was confirmed by X-ray investigations. The reaction of 20 c in aqueous HCl lead to the formation of 10-chloro-2-isopropyl-1,3,4,6,7,8-hexahydro-2H-benzo[g]isoquinolin-9-one (37 c). The structure of 37 c was verified by X-ray studies on single crystals.     

The crystal and molecular structure of the cycloadduct from an activated carbodiimide and methyl isothiocyanate

The crystal and molecular structures of the cycloadduct from isopropyl[α-(dimethylthio-carbamoyl)isopropyl]carbodiimide and methyl isothiocyanate were determined by single-crystal X-ray methods. The product was established to be 2-(1-isopropyl-3,5-dimethyl-4,6-dithioxo-hexahydro-1,3,5-triazine-2-ylidenamino)-N,N-dimethylthioisoburyramide, in which contrary to expectations based on hybridisation the heterocyclic ring adopts a boat conformation.     

Ultraviolet protection factors for clothing: an intercomparison of measurement systems

In recent years the need to standardize measurement protocols for quantifying the degree of ultraviolet radiation (UVR) protection provided by clothing has led to the introduction of a number of standards around the world. To date, these standards have specified spectral measurements of UVR transmission by clothing and fabrics. Development of a standard test method has become an important part of the testing process, and this article presents results from an intercomparison involving 10 independent testing laboratories and 11 different UVR transmission measurement instruments. In addition to comparing the measured ultraviolet protection factors (UPF), this intercomparison also incorporates detailed scan results from all 10 laboratories and highlights differences in performance of the various instruments in different wavelength regions. Careful examination of these differences can indicate where changes to the systems could be made to allow improvements both in equipment performance and in agreement of the final results. The variability in the measurements of UPF in this study suggest that the protection categories in standards may need to be broadened.     

Über die Darstellung von Arsendichloridtrifluorid,AsCl2F3

On the Preparation of Arsenic Dichloride Trifluoride, AsCl₂F₃ AsCl₂F₃ is prepared by pyrolysis of [AsCl₄]⁺ [AsF₆]^?. The vibrational spectra of the new low temperature compound are reported and the valence force constants are calculated. The formation of AsCl₂F₃ by ligand exchange reactions is discussed.     

Synthesis of Aristotelia-Type Alkaloids. Part XIII. Total syntheses of (+)-makonine, (+)-aristotelinone,and (+)-11,12-didehydroaristoteline

The oxidative transformation of synthetic (+)-aristoteline ((+)- 6 ) into other metabolites which had been isolated from Aristotelia species was investigated. Thus, treatment of (+)- 6 with I₂ as the single oxidant furnished the naturally occurring indole alkaloids (+)-makonine ((+)- 9 ),(+)-aristotelinone ((+)- 11 ), or (+)-11, 12-didehydroaristoteline ((+)- 7 ) in good yields, the selectivity of the oxidation process depending on the chosen reaction conditions.     

Über die Darstellung von Di(i-propyl)thiosulfonium-Salzen

On the Preparation of Di(i-propyl)thiosulfonium Salts [1] The preparation of the mercaptosulfonium salts (i-C₃H₇)₂SSX⁺SbCl₆^? (X = H, D) and of the chlorothiosulfonium salts (i-C₃H₇)₂SSCl⁺MF₆^? (M = As, Sb) and (i-C₃H₇)₂SSSCl⁺SbCl₆^? is reported. They are formed by reaction of chlorinated or protonated (i-C₃H₇)₂S with excess H₂S or SCl₂ and S₂Cl₂. The thiosulfonium compounds are characterized by vibrational and NMR spectroscopic methods.     

An electron-diffraction study of the molecular structure of gaseous perbromyl fluoride and calculation of its force field and vibrational amplitudes

The molecular structure of FBrO₃ has been studied by gas-phase electron diffraction. Least-squares refinements of the molecular geometry using fixed spectroscopic amplitudes revealed two geometrical minima. Initially, the amplitudes employed were derived from diagonal force fields obtained by spectroscopic least-squares refinements to fit observed and calculated wave numbers; for each geometry there are two spectroscopic minima. In the lowest geometrical minimum the wave number agreement is poor, however, the introduction of the ∠OBrO/∠FBrO interaction force constant removed the discrepancies; the resulting force field is F(Br-O) = 6.92 ± 0.02 mdyn Å^?1F(Br-F) = 3.22 ± 0.03 mdyn Å^?1, F(∠OBrO) = 1.06 ± 0.02 mdyn Å, F(∠FBrO) = 0.81 ± 0.03 mdyn Å, F(∠OBrO/∠FBrO) = ?0.19 ± 0.02 mdyn Å. In the corresponding geometrical minimum r_g(Br-O) = 1.582 ± 0.001 Å, r_g(Br-F) = 1.708 ± 0.003 Å, r_α(∠OBrO) = 114.9 ± 0.3°, r_α(∠FBrO) = 103.3 ± 0.3°. Perpendicular amplitude correction coefficients, calculated for each force field employed, were used throughout to relate the interatomic distances through the r_α-structure. The geometries of the r_α^o- and r_e-structures are estimated.