The U. V. spectrophotometric determination of potassium ethylxanthate

Summary A U. V.-spectrophotometric determination of potassium ethylxanthate is described and a recommended procedure is given. The method may be used for the determination of small amounts of carbon disulphide.

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Zusammenfassung Es wird eine UV-spektrophotometrische Bestimmung von Kaliumäthylxanthogenat beschrieben und eine Arbeitsvorschrift empfohlen. Die Methode kann für die Bestimmung kleiner Mengen Schwefelkohlenstoff verwendet werden.

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Résumé Une méthode U. V.-spectrophotométrique pour le dosage de l'éthylxanthogénate de potassium est décrite et une instruction recommendée est proposée. La méthode peut être utilisée pour le dosage des petites quantités de sulfure de carbone.

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Part of the thesis of the first author, Dissertation Free University, Amsterdam, 1956.     

Effect of diffusion on rates and molecular weights in graft polymerization

A theoretical analysis has been made of the graft polymerization process in terms of the quantitative interrelationship between the initiation rate R_i, the k_p/k_t^1/ ratio of the monomer, the equilibrium solubility M of the monomer in the polymer, the polymer film thickness L, and the diffusivity D of the monomer in the polymer. It is shown how the values of these parameters in any grafting system interact to lead to diffusion-controlled graft polymerization. Whether graft polymerization is diffusion-free or diffusion-controlled depends on the values of K_p, d, k_p/k_p^1/2, and L as gathered in the parameter A = [(K_p/k_t^1/2)R_i, D,/^1/2] L/2. When the values of the various terms are such that A is less than 0.1 (i.e., D is large while R_i, k_p, and L are small), the reaction is diffusion-free. When A is greater than 3 (i.e., D is small while R_i, k_p, and L are large), the reaction is diffusion-controlled. The derived equations showing the relationship between kinetic and diffusional parameters are theoretically applicable to all grafting systems, i.e., for all monomer-polymer combinations under all conditions of reaction temperature, radiation intensity and polymer film thickness. The theoretical analysis has been verified for the rate and degree of polymerization for the radiation-induced graft polymerization of styrene to polyethylene.     

Modification of the luminescence properties of an Europium(III) Tris(β-diketonate) Complex by Inclusion in γ-cyclodextrin and 2,3,6-trimethyl-γ-cyclodextrin

A 1:1 inclusion compound between octakis(2,3,6-tri-O-methyl)-γ-cyclodextrin (TRIMEG) and the chelate complex Eu(NTA)₃·2H₂O (NTA=1-(2-naphthoyl)-3,3,3-trifluoroacetonate) was prepared and characterized by powder X-ray diffraction, thermogravimetric analysis and photoluminescence spectroscopy. The results were compared with those obtained for the corresponding native γ-CD adduct. Excitation and emission spectra were measured, and the lifetimes were determined for the Eu³⁺ first excited state (⁵D₀). The results indicate the presence of only one low-symmetry environment for the Eu³⁺ cations in the inclusion compounds. Encapsulation of the Europium complex in the two CDs increases the quantum efficiency of the ligand-to-metal energy transfer pathway, but the efficiency of the Eu³⁺ sensitization was significantly higher with TRIMEG as the host molecule. This may be related with the observation that the two hosts appear to have different influences on the Eu³⁺ coordination environments for the guest molecule.     

On the viability of small endohedral hydrocarbon cage complexes: X@C4H4, X@C8H8, X@C8H14, X@C10H16, X@C12H12, AND X@C16H16

Small hydrocarbon complexes (X@cage) incorporating cage-centered endohedral atoms and ions (X = H(+), H, He, Ne, Ar, Li(0,+), Be(0,+,2+), Na(0,+), Mg(0,+,2+)) have been studied at the B3LYP/6-31G(d) hybrid HF/DFT level of theory. No tetrahedrane (C(4)H(4), T(d)()) endohedral complexes are minima, not even with the very small hydrogen atom or beryllium dication. Cubane (C(8)H(8), O(h)()) and bicyclo[2.2.2]octane (C(8)H(14), D(3)(h)()) minima are limited to encapsulating species smaller than Ne and Na(+). Despite its intermediate size, adamantane (C(10)H(16), T(d)()) can enclose a wide variety of endohedral atoms and ions including H, He, Ne, Li(0,+), Be(0,+,2+), Na(0,+), and Mg(2+). In contrast, the truncated tetrahedrane (C(12)H(12), T(d)()) encapsulates fewer species, while the D(4)(d)() symmetric C(16)H(16) hydrocarbon cage (see Table of Contents graphic) encapsulates all but the larger Be, Mg, and Mg(+) species. The host cages have more compact geometries when metal atoms, rather than cations, are inside. This is due to electron donation from the endohedral metals into C-C bonding and C-H antibonding cage molecular orbitals. The relative stabilities of endohedral minima are evaluated by comparing their energies (E(endo)) to the sum of their isolated components (E(inc) = E(endo) - E(cage) - E(x)) and to their exohedral isomer energies (E(isom) = E(endo) - E(exo)). Although exohedral binding is preferred to endohedral encapsulation without exception (i.e., E(isom) is always exothermic), Be(2+)@C(10)H(16) (T(d)(); -235.5 kcal/mol), Li(+)@C(12)H(12) (T(d)(); 50.2 kcal/mol), Be(2+)@C(12)H(12) (T(d)(); -181.2 kcal/mol), Mg(2+)@C(12)H(12) (T(d)(); -45.0 kcal/mol), Li(+)@C(16)H(16) (D(4)(d)(); 13.3 kcal/mol), Be(+)@C(16)H(16) (C(4)(v)(); 31.8 kcal/mol), Be(2+)@C(16)H(16) (D(4)(d)(); -239.2 kcal/mol), and Mg(2+)@C(16)H(16) (D(4)(d)(); -37.7 kcal/mol) are relatively stable as compared to experimentally known He@C(20)H(20) (I(h)()), which has an E(inc) = 37.9 kcal/mol and E(isom) = -35.4 kcal/mol. Overall, endohedral cage complexes with low parent cage strain energies, large cage internal cavity volumes, and a small, highly charged guest species are the most viable synthetic targets.     

Homonuclear transition-metal trimers

Density-functional theory has been used to determine the ground-state geometries and electronic states for homonuclear transition-metal trimers constrained to equilateral triangle geometries. This represents the first application of consistent theoretical methods to all of the ten 3d block transition-metal trimers, from scandium to zinc. A search of the potential surfaces yields the following electronic ground states and bond lengths: Sc3(2A1',2.83 A), Ti3(7E',2.32 A), V3(2E",2.06 A), Cr3(17E',2.92 A), Mn3(16A2',2.73 A), Fe3(11E",2.24 A), Co3(6E",2.18 A), Ni3(3A2",2.23 A), Cu3(2E',2.37 A), and Zn3(1A1',2.93 A). Vibrational frequencies, several low-lying electronic states, and trends in bond lengths and atomization energies are discussed. The predicted dissociation energies DeltaE(M3-->M2+M) are 49.4 kcal mol(-1)(Sc3), 64.3 kcal mol(-1)(Ti3), 60.7 kcal mol(-1)(V3), 11.5 kcal mol(-1)(Cr3), 32.4 kcal mol(-1)(Mn3), 61.5 kcal mol(-1)(Fe3), 78.0 kcal mol(-1)(Co3), 86.1 kcal mol(-1)(Ni3), 26.8 kcal mol(-1)(Cu3), and 4.5 kcal mol(-1)(Zn3).     

Reactivite des carbanions benzyliques : VIII. Etude de la structure d'alkyl-9 lithio-10 dihydro-9,10 anthracenes par rmn du proton et spectrometrie d'absorption electronique; influence du substituant,du solvant et de la temperature

The structure of the 9,10-dihydroanthracenyl anion and of a series of 9-alkyl-10-lithio-9-10-dihydroanthracenes (9-R-10-LiDHA, I–V where R = H, Me, Et, i-Pr, t-Bu) was studied in solution by electronic absortion spectrometry and proton magnetic resonance. Our electronic absorption results, in addition to those of other authors, show that the contact ion pairs (c.i.p.) have an absorption at λ_max}- 400 nm (I–III) and 415 nm (V) whereas the loose ion pairs (l.i.p.) absorb at λmax}- 450 nm (I–V). In the NMR the chemical shift of the proton para with respect to the carbanionic center was examined as a function of solvent (THF, THF/HMPA, and in some cases ether or pure HMPA) and temperature (+20 to ?40°C). The para proton is shielded significantly with regard to the aromatic protons of the hydrocarbon (Δδ(H_para) ca. 1–1.7 ppm). The weakest shielding was observed in ether, in agreement with the existence of c.i.p. The largest shielding (THF/HMPA or pure HMPA) is in connection with the presence of l.i.p. where the negative charge is less localised at position 10. Moreover, in the same solvent, and at the same temperature, Δδ(H_para) was observed to increase with the substituent bulk, up to the point that there are only l.i.p. present. As found previously (namely for the fluorenyl anion) the l.i.p./c.i.p. ratio increases when temperature decreases. The results of this structural study allow to rationalize the protonation stereochemistry of 9-alkyl-10-lithio-9,10-dihydroanthracenes in the above-mentioned solvents.     

Computational study of the aminolysis of esters. The reaction of methylformate with ammonia

The aminolysis of esters is a basic organic reaction considered as a model for the interaction of carbonyl group with nucleophiles. In the present computational study the different possible mechanistic pathways of the reaction are reinvestigated by applying higher level electronic structure theory, examining the general base catalysis by the nucleophile, and a more comprehensive study the solvent effect. Both the ab initio QCISD/6-31(d,p) method and density functional theory at the B3LYP/6-31G(d) level were employed to calculate the reaction pathways for the simplest model aminolysis reaction between methylformate and ammonia. Solvent effects were assessed by the PCM method. The results show that in the case of noncatalyzed aminolysis the addition/elimination stepwise mechanism involving two transition states and the concerted mechanism have very similar activation energies. However, in the case of catalyzed aminolysis by a second ammonia molecule the stepwise mechanism has a distinctly lower activation energy. All transition states in the catalyzed aminolysis are 10-17 kcal/mol lower than those for the uncatalyzed process.     

Hypervalency avoided: simple substituted BrF3 and BrF5 molecules. Structures, thermochemistry, and electron affinities of the bromine hydrogen fluorides HBrF2 and HBrF4

Five different pure density functional theory (DFT) and hybrid Hartree-Fock/DFT methods have been used to search for the molecular structures, thermochemistry, and electron affinities of the bromine hydrogen fluorides HBrF(n)/HBrF(n)(-) (n = 2, 4). The basis sets used in this work are of double-zeta plus polarization quality in conjunction with s- and p-type diffuse functions, labeled as DZP++. Structures with Br-F and Br-H normal bonds, that is, HBrF(2)/HBrF(2)(-) with C(2v) or C(s) symmetry and HBrF(4)/HBrF(4)(-) with C(4v) or C(s) symmetry, are genuine minima. However, unlike the original BrF(3) and BrF(5) molecules, the global minima for HBrF(n)/HBrF(n)(-) (n = 2, 4) species are predicted to be complexes, some of which contain hydrogen bonds. The demise of the hypervalent structures is due to the availability of favorable dissociation products involving HF, which has a much larger dissociation energy than F(2). Similar reasoning suggests that PF(4)H, SF(3)H, SF(5)H, ClF(2)H, ClF(4)H, AsF(4)H, SeF(3)H, and SeF(5)H will all be hydrogen bond structures incorporating diatomic HF. The most reasonable theoretical values of the adiabatic electron affinities (EA(ad)) are 3.69 (HBrF(2)) and 4.38 eV (HBrF(4)) with the BHLYP method. These electron affinities are comparable to those of the analogous molecules: Br(2)F(n), ClBrF(n), and BrF(n)(+1) systems. The first F-atom dissociation energies for the neutral global minima are 60 (HBrF(2)) and 49 kcal/mol (HBrF(4)) with the B3LYP method. The first H-atom dissociation energies for the same systems are 109 (HBrF(2)) and 116 kcal/mol (HBrF(4)). The large Br-H bond energies are not sufficient to render the hypervalent structures energetically tenable. The dissociation energies for the complexes to their fragments are relatively small.     

Dosage de traces de fer total dans les vins

Résumé Le dosage électrophotocolorimétrique des traces de fer total dans les vins au moyen de l'orthophénanthroline a été peu étudié jusqu'à présent. Sous un titre général le mémoire expose les conclusions auxquelles ont abouti diverses recherches consacrées à l'étude du dosage en question. L'application raisonnée de la méthode deBencze a permis d'établir une technique d'évaluation photocolorimétrique du fer dans les vins et les jus de fruits. Intéressante par sa simplicité et sa rapidité d'exécution, la technique en question indique le moyen de doser cet élément directement dans les liquides obtenus à partir des vins, suivant le procédé du traitement oxydatif au perhydrol. Ce traitement a permis de revaloriser le dosage du fer au point de vue de la rapidité par rapport à la minéralisation sèche, sans apporter en même temps des complications dans les manipulations analytiques et sans affecter la sensibilité et la précision de la réaction colorimétrique.

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Summary There has been little study of the electrophotocolorometric determination of the total iron content of wines by means of orthophenanthroline. Under a general title, the paper gives the general conclusions reached as a result of various studies of this determination. An intelligent application of theBencze method has resulted in a photocolorimetric evaluation of iron in wines and fruit juices. Characterized by simplicity and rapidity, this technique provides a means of determining this element directly in the liquids obtained from wines after oxidative treatment with perhydrol. This procedure compares, favorably with respect to speed with mineralization by the dry method, but is free from the complications in the analytical manipulations and there is no adverse effect on the sensitivity and the precision of the colorimetric reaction.

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Zusammenfassung Die elektrokolorimetrische Bestimmung der geringen Gesamtmengen an Eisen in Wein mit Hilfe von o-Phenanthrolin wurde bisher nur wenig untersucht. Die beim Studium dieses Verfahrens gesammelten Erfahrungen werden in Form eines allgemeinen Überblicks mitgeteilt. Die Anwendung der Methode vonBencze führte zur Ausarbeitung einer Arbeitsvorschrift zur kolorimetrischen Bestimmung des Eisens in Wein und Fruchtsäften. Diese ist wegen der Einfachheit und Geschwindigkeit ihrer Durchführung von praktischem Interesse. In der durch Oxydation des Weines mit Wasserstoffperoxyd erhaltenen Lösung kann das Eisen unmittelbar bestimmt werden. Diese Art des Aufschlusses ist besser geeignet als die trockene Veraschung, ohne die Empfindlichkeit oder die Genauigkeit der Farbreaktion zu beeinträchtigen.