Effects of concentrated matrices on the determination of trace levels of platinum and gold in aqueous samples using solvent extraction—Zeeman effect graphite furnace atomic absorption spectrometry and inductively coupled plasma—mass spectrometry

Two methods of determining trace levels of platinum and gold in aqueous solutions with high concents of total dissolved solids were investigated. The first involves preconcentration and separation of the precious metals from the interfering matrix by solvent extraction, followed by graphite furnace atomic absorption spectrometry (GFAAS) with Zeeman effect background correction. The direct determination of Pt and Au in solutions of high ionic strength by GFAAS is not desirable because of interference between elements in the matrix and the analyte, increased imprecision of analysis, greatly increased background absorbance leading to increased detection limits and rapid deterioration of the graphite tube. All the extraction methods for gold examined in this study resulted in decreased imprecision, increased sensitivity and lower background absorbance compared with direct measurements on the aqueous solution. All techniques also exhibited good recoveries (> 8%) and reproducibilities (relative standard deviation < 10%). The highest sensitivities for gold extraction from distilled water were obtained for dibutyl sulfide (DBS)—toluene and the lowest for cyanide—dibutyl ketone. The degree of extraction of Au was, however, dependent on the composition of the solution, indicating that standard and sample matrices should be closely matched even when employing solvent extraction. Solvent extraction was generally less successful for Pt. In order to obtain an acceptable imprecision in the Pt extractions, it was found that the use of SnCl₂ as a labilizing agent is essential for most of the techniques investigated.The second method was direct measurement by inductively coupled plasma mass spectrometry (ICP—MS). ICP—MS offers the advantages of a very low detection limit (100 ng l^?1 or better) without preconcentration and a large dynamic range. However, severe matrix effects can occur in concentrated solutions. Whereas high concentrations in solution of both sodium perchlorate and sodium chloride decrease the sensitivity, the presence of sulfide and natural organic (fulvic) acid increase the sensitivity for Pt and Au by a factor of up to 4. Sulfate, on the other hand, decreases the sensitivity of ICP-MS for Pt. The method of standard additions or isotope dilution is recommended for routine use to circumvent this problem, especially when the nature of the matrix is unknown or cannot be easily matched in the standards.     

Conductance study of association in aqueous CaCl2, Ca(CH3COO)2, and Ca(CH3COO)2.nCH3COOH from 348 to 523 K at 10 MPa

The conductances of aqueous CaCl2, Ca(CH3COO)2, and Ca(CH3COO)2.nCH3COOH were measured from 348 to 523 K at pressures near 10 MPa using a flow conductometric technique. The first association constant for calcium chloride and the first and second association constants for calcium acetate in water, were derived from a least-squares fit of the measurements to a conductance model in which activity coefficients were calculated using the mean spherical approximation (MSA) and the conductance was modeled by the Turq, Blum, Bernard, and Kunz (TBBK) equation, plus a mixture model.     

Sequence distribution and intramolecular excimer formation in styrene-acrylonitrile copolymers

Styrene-acrylonitrile copolymers, like many other copolymers containing styrene, exhibit both normal and excimer fluorescence. We have shown that the ratio of the excimer to monomer fluorescence intensities in random styrene-acrylonitrile copolymers is linearly dependent upon the concentration of styrene-styrene bonds in the copolymer. This observation is consistent with a photophysical model which allows the energy absorbed by styrene units to migrate freely along the copolymer chain. Some of the energy is emitted in the form of normal fluorescence; some of the energy, trapped by neighbouring styrene-styrene pairs suitably oriented to allow excimer formation, is emitted as excimer fluorescence. The fluorescence characteristics of acrylonitrile-styrene copolymers are contrasted with those of methyl methacrylate-styrene copolymers, in which the methylmethacrylate sequences are believed to present partial barriers to energy migration along the copolymer chains.     

Electronic interactions in tertiary oligophenylureas

The syntheses, structures, and spectroscopy of a series of oligomeric tertiary oligophenylureas possessing one to five phenyl rings are reported. A convergent synthetic method employing tertiary monoamine and diamine building blocks is employed. NMR and molecular modeling are indicative of folded structures for all of the oligophenylureas in which adjacent phenyl rings have a splayed face-to-face geometry. NMR chemical shifts, absorption and emission maxima, and electrochemical oxidation potentials are all dependent upon the number of phenyl rings. The addition of a first inner phenyl has a pronounced effect on the chemical shifts, while a second and third inner phenyl have diminished effects. The oxidation potentials of the oligophenylureas display an abrupt decrease upon the addition of the second inner phenyl. The absorption and emission spectra are relatively insensitive to the addition of one to three inner phenyl rings. The electronic structures of the oligophenylureas possessing one to eight rings have been analyzed using ZINDO calculations. The frontier orbitals of the ureas with one to three phenyl rings are localized on a single phenyl ring (the inner ring for the three-ring urea), whereas the frontier orbitals of the higher oligomers are delocalized over two phenyl rings. In all cases, urea-localized n,pi* transitions are lower in energy than the phenyl-localized pi,pi* transitions. The changes in properties with added phenyl rings parallel those previously observed for multilayered cyclophanes; however, they are less pronounced because of weaker coupling between the phenyl rings of the oligophenylureas.     

Rotational diffusion effects on absorbance measurements: limitations to the magic-angle approach.

Optical absorbance changes are commonly used to characterize intermediates which appear in the bleaching sequence of rhodopsin and in the photocycle of bacteriorhodopsin. Absorbance changes can be caused by an intermediate's rotational diffusion, and when this occurs it can distort absorbance changes due to the structural evolution of intermediates. Linear polarization of an optical probe source at 54.7 degrees (the magic angle) relative to the polarization direction of a linearly polarized actinic source has often been used to eliminate signals due to rotational diffusion. We used Jones calculus to investigate the validity of the magic-angle strategy. Taylor expansion of the result in powers of the absorbances of the bleached ground state and of the intermediates leads to a relatively simple expression which can be used to determine whether rotational contributions are likely under various experimental conditions. This expression shows that in first order no dichroism-dependent term appears in the absorbance measured at magic angle. In second order, however, linear dichroism contributes to signals. For the sequence of rhodopsin intermediates: rhodopsin hv----bathorhodopsin in equilibrium BSI----lumirhodopsin, where BSI is a recently discovered blue-shifted intermediate, we determined the magnitude of the dichroism signals to be, on average, less than 2% of the true absorbance change due to the intermediates themselves (and hence undetectable). Freedom from dichroism artifacts in this case results from the fact that the transition dipoles of these intermediates are similar to that of rhodopsin. Larger and certainly detectable dichroism signals are predicted to occur, even at the magic angle, for later intermediates which have transition dipole moments which differ significantly from that of rhodopsin.(ABSTRACT TRUNCATED AT 250 WORDS)     

Gyromagnetic ratios of excited states in186W

The gyromagnetic ratios of the 4 ₁ ⁺ , 6 ₁ ⁺ , and 2 ₂ ⁺ states in¹⁸⁶W were measured relative to that of the 2 ₁ ⁺ level by means of the transient field implantation perturbedγ-ray angular distribution technique. The nuclei in the states of interest were Coulomb excited using a beam of 220-MeV⁶³Cu projectiles and recoiled swiftly through a thin, polarized Fe foil. The present measurements yielded ratiosg(4 ₁ ⁺ )/g(2 ₁ ⁺ )=1.04±0.07,g(6 ₁ ⁺ )/g(2 ₁ ⁺ )=1.03 ±0.20 andg(2 ₂ ⁺ )/g(2 ₁ ⁺ )=0.63±0.13. The sizable disparity between the measuredg-factors of the ground- and excited-band is examined within the context of the interacting boson approximation model.