Vibrational analysis and normal coordinate analysis of trimethylphosphane

Raman spectra of trimethylphosphine {P(CH₃)₃} as liquid have been recorded with parallel and perpendicular polarization. Vibrational assignments are given by means of a normal coordinate analysis. The skeletal modes of the phosphoruscarbon-core and their interactions with the methyl groups, its force field and potential energy distribution are discussed.     

Kinetic analysis of derivative curves in thermal analysis

Two methods of obtaining kinetic parameters from derivative thermoanalytical curves are proposed. The methods are based on the general form of kinetic formulae and are applicable to general types of reactions governed by a single activation energy. One method utilizes the linear relation between peak temperature and heating rate in order to estimate the activation energy, and only the information of the rate of conversion versus the temperature is necessary. The other method needs the information of both the conversion and the rate of conversion versus the temperature, and the Arrhenius plot is made for an assumed kinetic mechanism.

     

Mercury analysis: a special example of species analysis

Summary Mercury species analysis requires the determination of numerous different compounds with very different behaviour regarding environment and toxicity. For these differing species several new and more sensitive analytical methods have been developed and tested. Mercury species cannot be detected directly in most cases, and are normally derivatized by different agents and determined by different detector systems. In a new HPLC method with photometric detection more than 10 different organomercurials could be analysed as their thio-ethanol complexes. By alkylation of mercury compounds they can be separated by GC and analysed with an AAS or AFS as detector. Volatile organic species of Hg can be separated on Carbotrap^®, where Hg⁰ is not adsorbed, and analysed thereafter. With atomic fluorescence the detection limit for Hg⁰ measurement is improved significantly when compared with the widely used atomic absorption method. Results obtained with this new method are shown and discussed. Future developments for species analysis are outlined; not only to analyse the covalent metal — carbon/oxygen compounds — primary species-analysis — but also compounds with ionic or complex bonding: secondary species-analysis. With these developments, prediction of species behaviour in the environment, including toxicity assessment and decontamination proposals, should be made possible.     

Multielemental analysis of soils by instrumental neutron activation analysis

The results of an instrumental neutron activation analysis of some elemental concentrations in different soil samples near the industrial areas at Tirupati, India, are reported. Altogether 14 elements, Sm, La, Cr, Co, Zn, Cs, Ce, Th, Rb, Na, K, Sr, Fe and Eu were determined. The samples were irradiated with neutrons at the 100 kW Triga - Mainz research reactor and the induced activities were measured by gamma-ray spectrometry using an efficiency calibrated high resolution high purity germanium (HPGe) detector in connection with a multichannel analyzer. The results are discussed.     

Characterization and analysis of waxes by differential thermal analysis

The characterization of waxes by differential thermal analysis is described. An endothermic peak at 475-480 degrees is characteristic of microcrystalline and polyethylene waxes, and measurement of its area provides a method for the estimation of these waxes in mixtures.     

Elemental analysis of limestone by instrumental neutron activation analysis

Limestone samples from Assuit Governrate in Upper Egypt were subjected to elemental analysis by instrumental neutron activation analysis and X-ray fluorescence techniques. The samples were properly prepared together with their standards and simultaneously irradiated in a neutron flux of the order 7 × 1011 n/cm² s using TRIGA research reactor at Mainz. After activation the samples were subjected to γ-ray spectrometry using a high purity germanium detection system and computerized multichannel analyzer. Nineteen elements: Na, Ca, Mn, Fe, Sc, Cr, Co, Zn, Sn, La, Ce, Nd, Eu, Sm, Yb, Lu, Hf, Th and U were analyzed. X-ray fluorescence spectrometry have been also used. The presence of any elements in higher or lower levels in certain limestone samples is contingent on the occurrence of its bearing minerals, nature of parent sediments and depositional environments of these sediments. The major elements in the samples were also observed to be among the elements that had high enrichment factors in the study of suspended dust particulate within and around cement industries. This confirms cement as the major contributor to the airborne particulate matter in the environs.     

Application of multidimensional spectrum analysis for neutron activation analysis

Feasibility of the method of multidimensional -ray spectrometer for neutron activation analysis was examined. Reference igneous rock (JP-1, JB-1a and JB-1) samples issued by the Geological Survey of Japan (GSJ) and the Allende meteorite reference sample were irradiated in a research reactor, and multiple -rays from the produced radioisotopes via neutron capture reactions were measured using an array of twelve germanium detectors with BGO Compton suppressors called GEMINI. Simultaneously thirty elements were observed with no chemical separation. The observed smallest component was Eu contained in JP-1 with abundance of 4 ppb.     

Slope analysis and scaling analysis of electrodeposited thin films

We introduce slope analysis as a straightforward complement to scaling analysis for characterizing the morphology of electrodeposited thin films. The surface slope θ, defined as the angle between the local surface normal and the film normal, is calculated as a function of position for electrodeposited Cu films of increasing thickness t. We show that the mean value of θ increases with t and demonstrate the close relationship between this observation and the increase in local roughness found in previous studies from scaling analysis.     

Processing and error analysis of signals in flow-injection analysis

The processing and error analysis of signals in flow-injection systems were systematically studied by simulation and experimental measurements. The content includes an error analysis for peak-height and peak-area signal, a least-squares filtering procedure applied to the flow-injection curve and a peak recognition to remove interferences from air bubbles. Simulation results were obtained by statistical processing of peak-height and peak-area values from Gaussian curves to which noise had been added. The experimental measurements were done by an automatic flow-injection device to obtain detailed information for each individual point of a peak. 2-(2-Arsenophenylazo)-7-(2,6-dichlorophenylazo-4-sulphonic acid)-1,8-dihydroxynaphthalene-3,6-disulphonic acid (DCSA) was used for measuring physical dispersion alone, and Fe(II)-o-phenanthroline for the measurement of both physical dispersion and chemical reaction. The results from computer simulation and experiments agreed well.     

Multielement analysis of lichen by instrumental neutron activation analysis

Lichen (species Trypethelium Eluteriae) is analysed for different elements. Nondestructive instrumental neutron activation analysis is employed for the multielemental analysis. Gamma-ray spectrometry is used for the identification and quantitative estimation of elements. Concentrations of 24 elements are reported. Gamma-ray spectrum of the lichen irradiated for 16 hours, delayed for 10 days, and counted for 10 hours on a 50 cm³ coaxial Ge(Li) detector is given.     

The analysis of art through the art of analysis

The diversity of materials that have been employed in the manufacture of cultural objects calls for a boundless variety of analytical methods. Constraints on sampling result in a preference for non-destructive or micro-techniques.     

CE-based analysis of hemoglobin and its applications in clinical analysis

This review focuses on the developments and trends in CE including CIEF, CZE, MEKC, two-dimensional conjunction of CIEF-capillary gel electrophoresis, and MEKC-CZE on microfluidic devices coupled to different detection approaches, such as UV absorbance, LIF, MS, and chemiluminescence etc. for performing analysis of hemoglobin (Hb), also with an emphasis on its applications in clinical analysis. Analysis of human Hb is of important clinical sense for numerous hemoglobinopathies associated with the congenital defects and abnormal contents of Hb. The diversiform modes render CE a comprehensive primary clinical tool for Hb analysis, which is rapid, sensitive, high-resolution, and not labor-intensive.     

Trace-element analysis of argyle diamonds using instrumental neutron activation analysis

Thirty four elements were determined by instrumental neutron activation analysis in colourless, brown, and pink diamonds, with and without inclusions. These were compared with data obtained for similar elements in the host lamproite rock. The natural radioactivity of these samples was measured by instrumental techniques, and found to be negligible.     

Kinetic analysis of catalytic slurry oil pyrolysis using thermogravimetric analysis

Journal of Thermal Analysis and Calorimetry - Pyrolysis is an important process for converting unconventional fuels, such as heavy oil, residues and oil sand, to high-value-added light products....     

Stepwise injection analysis as a new method of flow analysis

Various versions of flow analysis techniques (continuous-flow, flow-injection, and sequential-injection analysis) and their relative advantages and disadvantages are considered. Cyclic (stepwise) injection analysis is proposed, and the general principles of this technique are described.     

Instrumental neutron activation analysis for the elemental analysis of cement

Cement is widely used as a construction material in Libya. Production plants introduce certain contaminants to the environment. The dust from such plants is carried away to neighbouring areas. This dust contains a substantial amount of contaminants depending on the origin of clays used in the production. In this study, a survey of elemental concentration of clay and cement was carried out to assess the environmental impact of such plants, especially those that are situated near residential and agricultural areas. Cement and clay samples, imported and locally produced, were analyzed. Instrumental neutron activation analysis was utilized to determine the elemental concentration of As, Ca, Ce, Co, Cr, Eu, Fe, Hf, La, Na, Rb, Sb, Sc, Sm, Ta, Th, U, Yb and Zn. Elevated concentrations of U and Th were found in a number of cement samples. The two nuclides are part of an elaborate decay scheme producing a range of radioactive elements, which emit alpha-, beta- and gamma-radiation. With ⁴⁰K, they could give elevated levels of background radiation in buildings resulting in higher exposure doses. This could pose a health hazard and a detrimental effect on the well being of residents, especially in poor ventillated buildings. Also, cement is the main component for constructing underground reservoirs for collecting rainwater for drinking in private residences, so some harmful elements could leach into water. This is the first comprehensive survey of commercial cement brands and clays used in Libya. These results are intended to build a database for trace element concentrations using INAA.     

Kinetic analysis of complex decomposition reactions using evolved gas analysis

For complex decomposition reactions, traditional methods, such as TG and DSC cannot fully resolve all of the steps in the reaction. Evolved gas analysis (EGA) offers another tool to provide more information about the decomposition mechanism. The decomposition of sodium bicarbonate was studied by TG, DSC and EGA using a simultaneous thermal analysis unit coupled to a FTIR. The decomposition of sodium bicarbonate involves two reaction products H₂O and CO₂, which are not evident from either TG or DSC measurements alone. A comparison of the reaction kinetics from TG, DTG and EGA data were compared.     

Compositional analysis of American southwestern ceramics by neutron activation analysis

Mercury, a known neurotoxin, has been implicated in the etiology and pathogenesis of such disease states as Alzheimer's and Parkinson's diseases. There is concern that the exposure to mercury vapor released from dental amalgam restorations is a potential health hazard. Measurement of mercury concentrations in blood or urine may be useful in diagnosis of mercury poisoning and in assessing the extent of exposure. This study describes the optimization of pre-neutron activation analysis procedures such as sampling, selection of irradiation and counting vials and acid digestion in order to minimize mercury loss via volatilization and/or permeation through containers. Therefore, the determination of mercury can be complicated by these potential losses. In the optimized procedure 20 mL of urine was spiked with three different concentrations of mercury, digested with concentrated nitric acid, and placed in polypropylene vials for irradiation and counting. Analysis was performed by subtracting the Se-75 photopeak contribution to the 279 keV Hg-203 photopeak and applying the method of standard additions. Urinary mercury concentrations in normal human subjects were determined to be of the order of 10 ng/mL.     

Experimental comparison of flow-injection analysis and air-segmented continuous flow analysis

A miniature continuous flow analyzer that can be configured for either air-segmented continuous flow analysis (c.f.a.) or flow-injection analysis (f.i.a.) was used to compare the performance of the two techniques in terms of sampling rates, samples and reagent consumption factors and analtical precision. Details of simply dye dispersion experiments and spectrophotometric chloride determinations are presented. Chloride determinations at rates of up to 360 determinations per hour could be achieved with either technique; sample and reagent consumption was less for the air-segmented flow system than for flow-injection systems equipped with either coiled open tubular reactors (0.05 cm i.d.) or single-bead-string reactors. The advantages of single-bead-string reactors for determinations by merging-zones f.i.a. are demonstrated. The c.f.a. and f.i.a. techniques are shown to be complementary, and the relative merits of each for various applications are discussed.     

Application of factor analysis for resolving thermogravimetric-mass spectrometric analysis spectra

Factor Analysis was used for extracting information out of the mixture mass spectra recorded in a thermogravimetric-mass spectrometric analysis. Principal component analysis (PCA) and a special diagram, the contour variance diagram (ContVarDia), were used for performing the factor analysis. The method was applied for studying the thermal decomposition of Kraton 1107 copolymer. Pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS) was used for identification of the pyrolysis products of Kraton 1107. The application of factor analysis resulted in the determination of the main thermal decomposition steps and the prediction of the mass spectrum corresponding to each step. Those mass spectra were either pure spectra corresponding to main evolved gases or average spectra corresponding to multiple gases evolved in one decomposition step. The advantages and the limitations of the chemometric approach were discussed.