Classification of the distribution of trace impurities by spark source mass spectrometry analysis

Spark source mass spectrometry in combination with principal component analysis and clustering analysis was used to investigate the trace element distributions in metallic samples. The analysis of Zn and Cu samples and a comparison with direct imaging secondary ion microscopy demonstrated the consistency of the approach.On leave from Department of Chemistry, Nanjing Normal University, Nanjing, People's Republic of China.     

Longitudinal field quenching studies in KCl and KBr — Evidence for a precursor muonium state

The repolarization of μ⁺ in a longitudinal field as a function of field strength has been measured at various temperatures in KCl and KBr single crystals. The data at room temperature in KCl are essentially in agreement with Ivanteret al. /1/ and Nishiyamaet al. /5/. The obtained quenching curves can be reasonably fitted by assuming that the long lived muonium state, seen directly in transverse field experiments by Kieflet al. /4/, is preceded by another short lived muonium state with reduced hf-coupling. It is also necessary to allow for electron spin exchange in the precursor state. The model fits yield the hyperfine frequency of the precursor state, its chemical lifetime and an electron spin flip rate. It is speculated that the precursor state and the temperature dependence of the fitted parameters reflect the early history of the μ⁺ in its terminal spur.     

Mesomorphism of lanthanide-containing Schiff's base complexes with chloride counterions

Liquid crystalline complexes [Ln(LH) 3 Cl 3 ] have been synthesized, where Ln is a trivalent lanthanide ion (Pr-Lu, except Pm) and where LH is the Schiff's base ligand N -octadecyl4-tetradecyloxysalicylaldimine. Although the ligand does not exhibit mesomorphism, the complexes do (SmA phase). The mesophase behaviour of these compounds has been investigated by polarizing optical microscopy, differential scanning calorimetry and high temperature X-ray diffraction. The lanthanide complexes have much higher melting and clearing points than comparable complexes with nitrate or dodecyl sulphate counterions. In addition, the transition temperatures are virtually independent of the type of lanthanide ion. This behaviour is opposite to that observed for similar complexes with nitrate counterions [Ln(LH) 3 (NO 3 ) 3 ]. The differences in temperature dependence can be related to structural differences. Whereas in the nitrate complexes the Schiff's base ligand binds in a zwitterionic form, two-dimensional 1H NMR correlation spectroscopy (COSY) of [Lu(LH) 3 Cl 3 ] gives an indication that in the chloride complexes, besides coordination via the oxygen of molecules in the zwitterionic form, some of the Schiff's base ligands bind in a bidentate fashion (via the phenolic oxygen and the imine nitrogen).     

Diffuse reflection and polarization modulation FT-IR spectrometry of surface species

Summary Two techniques for measuring the infrared spectra of adsorbed species on surfaces of different types are described. Diffuse reflectance spectra of species adsorbed on powdered substrates with a high surface area can be measured with an exceptionally high signal-to-noise ratio. The technique is illustrated by the adsorption of carbon monoxide on rhodium supported on alumina at metal loadings between 0.1 and 10%. Some doubt is cast on previous band assignments for adsorbed CO molecules. Grazing incidence reflection-absorption spectrometry can be used to measure the spectra of molecules on flat metallic substrates of very low surface area. Attempts to develop a technique for observing the intermolecular vibration between the adsorbate and the substrate using a unique triple modulation approach are discussed.

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FT-IR-Spektrometrie mit diffuser Reflexions- und Polari-sations-Modulation von Adsorbaten an Oberflächen

Zusammenfassung Zwei Techniken zur Messung von Infrarot-Spektren von Adsorbaten verschiedener Art werden beschrieben. Diffuse Reflexionsspektren von Adsorbaten an pulverförmigen Substraten mit einer großen Oberfläche können mit einem außerordentlich großen Signal-zu-RauschVerhältnis gemessen werden. Als Beispiel dient die Adsorption von Kohlenstoffmonoxid an Rhodium auf Aluminiumoxid bei Metallgehalten von 0,1 bis 10%. Einige Zweifel an früheren Bandzuweisungen für adsorbierte CO-Moleküle werden geäußert. Reflexions-Absorptions-Spektrometrie mit streifendem Einfall kann zur Messung der Spektren von Molekülen an flachen metallischen Substraten mit sehr geringer Oberfläche benutzt werden. Versuche zur Entwicklung einer Technik für die Beobachtung der intermolekularen Schwingungen zwischen dem Adsorbaten und dem Substrat mittels einer einzigartigen Dreifach-Modulationstechnik werden diskutiert.

     

The population-sample decomposition approach to multivariate estimation methods

In this paper it is argued that all multivariate estimation methods, such as OLS regression, simultaneous linear equations systems and, more widely, what are known as LISREL methods, have merit as geometric approximation methods, even if the observations are not drawn from a multivariate normal parent distribution and consequently cannot be viewed as ML estimators. It is shown that for large samples the asymptotical distribution of any estimator, being a totally differentiable covariance function, may be assessed by the δ method. Finally, we stress that the design of the sample and a priori knowledge about the parent distribution may be incorporated to obtain more specific results. It turns out that some fairly traditional assumptions, such as assuming some variables to be non-random, fixed over repeated samples, or the existence of a parent normal distribution, may have dramatic effects on the assessment of standard deviations and confidence bounds, if such assumptions are not realistic. The method elaborated by us does not make use of such assumptions.     

Laser marked shadowgraphy: a novel optical planar technique for the study of microbubbles and droplets

A novel combination of backlighting and glare point velocimetry and sizing (GPVS) is proposed to measure the size distribution of microbubbles (or microdroplets). This new technique, which we will call laser marked shadowgraphy, avoids sizing out-of-focus bubbles (or droplets) and the associated bias error. Compared to backlighting, this combination also improves the precision of the diameter measurement and allows void fraction measurements. Compared with GPVS, a more robust image processing is obtained. The applicability of the developed technique is demonstrated on a cloud of electrochemically generated hydrogen bubbles.     

57Co implanted in reactive and non-reactive frozen gases

⁵⁷Co was implanted in different reactive and non reactive frozen gases like Ne, Ar, N₂, Xe, CH₄ and C₂H₄. Higher ionization states of Fe and cryochemical compounds are detected.     

Electron transfer reactions between vinylmagnesium bromide and phenyl-substituted methyl chlorides

The reaction of vinylmagnesium bromide ( 1 ) with trityl chloride ( 2 ) was investigated and the products were identified as triphenylmethane ( 3 ) (81 %), acetylene ( 4 ) (74%), trityl peroxide ( 6 ) (4%), and minute amounts of triphenylpropene ( 7 ) and p-diphenylmethyltetraphenylmethane ( 8 ). The results indicate that 1 possesses reducing property. The reaction mixture showed an ESR spectrum identical with that for trityl radical and the CIDNP of enhanced absorption for 4-H of l-diphenylmethylene-4-trityl-2,5-cyclohexadiene ( 9 ). Trapping experiment with styrene decreased the amount of 3 but had no effect on the formation of 4. The reducing property of 1 is discussed and one electron transfer mechanism for the reaction of 1 with 2 is proposed. S-T₀ mixing between trityl and·MgBr occurred and the coupling of polarized trityl radical with another trityl radical resulted in the formation of polarized dimeric product. The different character between the reaction of 1 and 2 and that of 1 and diphenylmethyl chloride ( 10 ) may be rationalized by the different electron-accepting abilities between 2 and 10. The origin of CIDNP effect shown by the product tetraphenylethane ( 11 ) for the reaction of 1 with 10 is also explained according to Kaptein's sign rule.