High-Resolution,Higher-Order UV/VIS Derivative Spectrophotometry

Derivative spectrophotometry has gained increasing importance in the past two years and is currently experiencing vigorous development. Following and introduction the present article provides a review of this extremely effective method. In particular, the advantages of higher-order derivative spectrophotometry (HODS method, n > 2) are discussed on the basis of practical examples from a wide range of analytical fields. The results are achieved with the aid of a newly developed analog computer unit, whereby for the first time readily reproducible, low-noise, on-line spectra can be obtained up to the 7th order and even, in favorable cases, up to the 9th order. In practice it has proved valuable to work with spectra of the 3rd to 5th order; but even higher derivations could be profitable for the separation of strongly superposed signals or for “fingerprinting”.     

Fourth-order diagrammatic MB-RSPT calculations of the interaction energy between two helium atoms

The efficiency of the MB-RSPT in the calculations of the correlation contributions to the interaction energies was investigated, using He₂ as a model Van der Waals system. The attention has been focused on the convergency of the perturbation expansion in the calculations of the interaction energy and on the analysis of the fourth-order terms of MB-RSPT. The rôle of the renormalization term in the correct long-range behaviour of the interaction potential has been emphasized.     

Spin density distributions in radical anions of heterocyclic amine N-oxides

The unrestricted Hartree-Fock (UHF) method of Snyder and Amos is used to calculate, in the -electron approximation, the spin density distributions in radical anions of heterocyclic amine N-oxides. The computed spin densities are observed to be in good agreement with the experimental values. The computed spin density distribution of the radical anion of pyridine N-oxide is consistent with the greater susceptibility of pyridine N-oxide relative to pyridine to electrophilic nitration. Also, the calculations are consistent with the lower basicity of the N-oxides relative to the parent bases.     

Chemical applications of group theory and topology

The following procedure is described for investigating the qualitative dynamics of simple chemical systems: 1) A so-called influence diagram is generated representing the relationships between the reference reactants (phase-determining intermediates); 2) This influence diagram is used to generate a truth table indicating possible transitions between state vectors representing the signs of the time derivatives of of the reference reactant concentrations; 3) The truth table is used to determine a state transition diagram representing the flow topology around unstable equilibrium points; 4) The characteristic equation of the adjacency matrix of the influence diagram is solved in order to determine the presence of such unstable equilibrium points. The two types of qualitative dynamics possible for chemical systems containing two reference reactants and one feedback circuit are bifurcation between two attracting regions (bistability) and limit cycle oscillation. However, in two reference reactant systems oscillation requires an additional self-activating loop to generate the unstable equilibrium point required for its realization. Bistability and limit cycle oscillation are also two of the possible types of qualitative dynamics for chemical systems containing three reference reactants. However, chemical systems with three reference reactants and two or more feedback circuits can also contain interlocking limit cycles, which can lead to toroidal oscillations or chaos. The influence diagrams are given for the systems exhibiting these various types of dynamic behavior along with a summary of the important properties of all 729 possible influences for simple chemical systems containing three reference reactants.     

AN INVESTIGATION ON THE ab initio CALCULATION OF INTERMOLECULAR INTERACTION——NON-BONDED INTERACTION IN THE HYDROGEN BOND COMPLEX (HF)_2

An ab initio calculation of the hydrogen bond complex (HF)_2 is given with the 6-311 G~(**) basis set, according to which the potential surface around the balance point of the distancès and the orientations between two HF molecules is obtained. The atomic charges in the system are calculated with the PD/LSF method (potential-derived/least-square-fitting method) and then an analysis of the hydrogen bond interaction between two HF molecules is given with the (exp-6-1) potential function, by means of which it is shown that the main interaction between them is not an electro-static but a charge transfer one. The potential curve between two HF molecules is like a Morse function.     

Pervaporative transport modelling in a ternary system: ethyltertiarybutylether/ethanol/polyurethaneimide

The study deals with the analysis of diffusion and mass transfer modelling during pervaporation in a true ternary system involving a polar liquid mixture (ETBE/EtOH) and a polar block copolymer (polyurethaneimide or PUI). A survey of methods of pervaporative transfer modelling in ternary systems is first developed. From differential permeation experiments carried out with both pure liquids, it appears that both permeants obey a Fickian law. Moreover, the diffusional behaviour is consistent with Long's model, which has thus been assumed for the related ternary system. An extension of the Brun's model is then derived, which takes into account the diffusion coupling as well the significant deviation from sorption ideality. From a practical point of view, the calculated values of fluxes show generally good agreement with the experimental results, although a small deviation occurs for mixtures of low ethanol content. Diffusion coefficients of both pure solvents corresponding to transient or steady state are compared. A very good agreement is found for the aprotic permeant (ETBE). whereas the diffusion coefficient of ethanol in transient state is only the quarter of the value corresponding to steady state. The results are discussed in comparison with related investigations in the literature, involving specific liquid-polymer interactions.     

Determination of Aroma Compounds in Blackberry by GC/MS Analysis

The aromatic composition of five blackberry cultivars (Bursa 2, Navaho, Nessy, Chester Thornless, and Jumbo) was studied. The Im-SPME (Immersion Solid Phase Micro Extraction) extraction technique was applied and the samples were analyzed by GC/MS. Furfural and its derivatives were found to be the major aromatic compounds and 5-hydroxymethylfurfural was the most abundant compound in all the blackberry varieties.     

Die Berechnung von Einelektronen-Integralen in der SCF-Xα-SW-Methode: I. Die Normierung

A normalization of the wave functions by means of the theoretical exact Multiple-Scattering-(MS)-formalism is discussed within the framework of the SCF-X-SW-method. For the atomic and extramolecular regions the integrals of normalization can be easily determined and the results can be described by the corresponding electronic charges. The calculation of the integral of the interatomic region is problematic. The needful volume integration is only necessary to theGreen's functions of the wave functions and can be solved by means of the residual theory. The further analytical calculation of the surface integrals leads to a complicated formalism which can be numerically evaluated.

     

Determination of rare earth impurities in high purity uranium by isotope dilution analysis

Summary An isotope dilution method for the determination of rare earth impurities in uranium has been developed and Ce, Nd, Sm, Eu and Gd have been determined in uranium oxide samples. The method involves isotopic dilution with enriched isotopes of the rare earths being measured, followed by the separation of rare earths from uranium. A mass spectrometer with thermionic source was used to determine the relative isotopic abundances in each of these rare earths. All these five elements were analysed selectively by preferential evaporation technique. Trace concentrations down to parts per billion range can be measured with good sensitivity and accuracy.

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Bestimmung von Verunreinigungen an Seltenen Erden in hochreinem Uran durch Isotopenverdünnungsanalyse

Zusammenfassung Eine Isotopenverdünnungsmethode wurde ausgearbeitet zur Bestimmung von Ce, Nd, Sm, Eu und Gd in Uranoxidproben. Das Verfahren umfaßt isotopische Verdünnung mit angereicherten Isotopen der zu bestimmenden Elemente und nachfolgende Abtrennung der Seltenen Erden von Uran. Die relativen Isotopenhäufigkeiten wurden mit Hilfe eines Massenspektrometers mit thermischer Ionenquelle bestimmt. Alle fünf Elemente wurden durch selektive Verdampfung analysiert. Spurenkonzentrationen bis herab zum ppb-Bereich konnten mit guter Empfindlichkeit und Genauigkeit erfaßt werden.

     

On the configuration interaction method for singlet states

The direct CI method, which avoids explicit calculation of the Hamiltonian matrix, is presented in a new form. The method is linked with Davidson's algorithm for iterative evaluation of the ground state eigenvector. The viability of the method is indicated by the test calculations on water which are described.