Stability constants and thermodynamic parameters of cadmium complexes with sulfonamides and cephapirin

Stability constant (log beta) and thermodynamic parameters of Cd2+ complexes with sulfonamide and cephapirin were determined by Polarographic technique at pH = 7.30 ± 0.01 and µ = 1.0 M KNO3 at 250°C. The sulfonamides were sulfadiazine, sulfisoxazole, sulfamethaxazole, sulfamethazine, sulfathiazole, sulfacetamide and sulfanilamide used as primary ligands and cephapirin as secondary ligand. Cd2+ formed 1:1:1, 1:2:1 and 1:1:2 complexes. The nature of electrode processes were reversible and diffusion controlled. The stability constants and thermodynamic parameters (deltaG, deltaH and deltaS) were determined. The formation of the metal complexes has been found to be spontaneous, exothermic in nature, and entropically unfavourable at higher temperature.

Solid phase extraction of zinc with octadecyl silica membrane disks modified by N,N'-disalicylidene-1,2-phenylendiamine and determination by flame atomic absorption spectrometry

A procedure for separation and preconcentration of trace amounts of Zn(II) from aqueous media is proposed. The procedure is based on the adsorption of Zn2+ on octadecyl bonded silica membrane disk modified with N,N'-disalicylidene-1,2-phenylendiamine at pH 7. The retained zinc ions were then stripped from the disk with a minimal amount of 1.5 mol L-1 hydrochloric acid solution as eluent, and determined by flame atomic absorption spectrometry. Maximum capacity of the membrane disk modified with 5 mg of the ligand was found to be 226 µg Zn2+. The relative standard deviation of zinc for ten replicate extraction of 10 µg zinc from 1000 mL samples was 1.2%. The limit of detection of the proposed method was 14 ng of Zn2+ per 1000 mL. The method was successfully applied to the determination of zinc in natural water samples and accuracy was examined by recovery experiments and independent analysis by graphite furnace atomic absorption spectrometry (GFAAS).

Magnetic Resonance Experiments with Atomic Hydrogen

In this thesis three experiments with atomic hydrogen (H) at low temperatures T<1 K are presented. Experiments were carried out with two- (2D) and three-dimensional (3D) H gas, and with H atoms trapped in solid H2 matrix. The main focus of this work is on interatomic interactions, which have certain specific features in these three systems considered. A common feature is the very high density of atomic hydrogen, the systems are close to quantum degeneracy. Short range interactions in collisions between atoms are important in gaseous H. The system of H in H₂ differ dramatically because atoms remain fixed in the H₂ lattice and properties are governed by long-range interactions with the solid matrix and with H atoms. The main tools in our studies were the methods of magnetic resonance, with electron spin resonance (ESR) at 128 GHz being used as the principal detection method. For the first time in experiments with H in high magnetic fields and at low temperatures we combined ESR and NMR to perform electron-nuclear double resonance (ENDOR) as well as coherent two-photon spectroscopy. This allowed to distinguish between different types of interactions in the magnetic resonance spectra. Experiments with 2D H gas utilized the thermal compression method in homogeneous magnetic field, developed in our laboratory. In this work methods were developed for direct studies of 3D H at high density, and for creating high density samples of H in H₂. We measured magnetic resonance line shifts due to collisions in the 2D and 3D H gases. First we observed that the cold collision shift in 2D H gas composed of atoms in a single hyperfine state is much smaller than predicted by the mean-field theory. This motivated us to carry out similar experiments with 3D H. In 3D H the cold collision shift was found to be an order of magnitude smaller for atoms in a single hyperfine state than that for a mixture of atoms in two different hyperfine states. The collisional shifts were found to be in fair agreement with the theory, which takes into account symmetrization of the wave functions of the colliding atoms. The origin of the small shift in the 2D H composed of single hyperfine state atoms is not yet understood. The measurement of the shift in 3D H provides experimental determination for the difference of the scattering lengths of ground state atoms. The experiment with H atoms captured in H2 matrix at temperatures below 1 K originated from our work with H gas. We found out that samples of H in H2 were formed during recombination of gas phase H, enabling sample preparation at temperatures below 0.5 K. Alternatively, we created the samples by electron impact dissociation of H₂ molecules in situ in the solid. By the latter method we reached highest densities of H atoms reported so far, 3.5(5)x10¹⁹ cm^-3. The H atoms were found to be stable for weeks at temperatures below 0.5 K. The observation of dipolar interaction effects provides a verification for the density measurement. Our results point to two different sites for H atoms in H2 lattice. The steady-state nuclear polarizations of the atoms were found to be non-thermal. The possibility for further increase of the impurity H density is considered. At higher densities and lower temperatures it might be possible to observe phenomena related to quantum degeneracy in solid.

Mathematical equation correction to spectral and transport interferences in high-resolution continuum source flame atomic absorption spectrometry: determination of lead in phosphoric acid

In this work, a new mathematical equation correction approach for overcoming spectral and transport interferences was proposed. The proposal was applied to eliminate spectral interference caused by PO molecules at the 217.0005 nm Pb line, and the transport interference caused by variations in phosphoric acid concentrations. Correction may be necessary at 217.0005 nm to account for the contribution of PO, since Atotal217.0005 nm = A Pb217.0005 nm + A PO217.0005 nm. This may be easily done by measuring other PO wavelengths (e.g. 217.0458 nm) and calculating the relative contribution of PO absorbance (A PO) to the total absorbance (Atotal) at 217.0005 nm: A Pb217.0005 nm = Atotal217.0005 nm - A PO217.0005 nm = Atotal217.0005 nm - k (A PO217.0458 nm). The correction factor k is calculated from slopes of calibration curves built up for phosphorous (P) standard solutions measured at 217.0005 and 217.0458 nm, i.e. k = (slope217.0005 nm/slope217.0458 nm). For wavelength integrated absorbance of 3 pixels, sample aspiration rate of 5.0 ml min-1, analytical curves in the 0.1 - 1.0 mg L-1 Pb range with linearity better than 0.9990 were consistently obtained. Calibration curves for P at 217.0005 and 217.0458 nm with linearity better than 0.998 were obtained. Relative standard deviations (RSD) of measurements (n = 12) in the range of 1.4 - 4.3% and 2.0 - 6.0% without and with mathematical equation correction approach were obtained respectively. The limit of detection calculated to analytical line at 217.0005 nm was 10 µg L-1 Pb. Recoveries for Pb spikes were in the 97.5 - 100% and 105 - 230% intervals with and without mathematical equation correction approach, respectively.

Estimation of standard enthalpy of formation of alkanes in gaseous state by calculating size, structural and electronic parameters in the molecules

A quantitative analysis is made on the correlation ship of thermodynamic property, i.e., standard enthalpy of formation (ΔH fº) with Kier's molecular connectivity index(¹Xv),vander waal's volume (Vw) electrotopological state index (E) and refractotopological state index (R) in gaseous state of alkanes. The regression analysis reveals a significant linear correlation of standard enthalpy of formation (ΔH fº) with ¹Xv, Vw, E and R. The equations obtained by regression analysis may be used to estimate standard enthalpy of formation (ΔH fº) of alkanes in gaseous state.

Determination of copper at wide range concentrations using instrumental features of high-resolution continuum source flame atomic absorption spectrometry

This work describes a method to determine Cu at wide range concentrations in a single run without need of further dilutions employing high-resolution continuum source flame atomic absorption spectrometry. Different atomic lines for Cu at 324.754 nm, 327.396 nm, 222.570 nm, 249.215 nm and 224.426 nm were evaluated and main figures of merit established. Absorbance measurements at 324.754 nm, 249.215 nm and 224.426 nm allows the determination of Cu in the 0.07 - 5.0 mg L-1, 5.0 - 100 mg L-1 and 100 - 800 mg L-1 concentration intervals respectively with linear correlation coefficients better than 0.998. Limits of detection were 21 µg L-1, 310 µg L-1 and 1400 µg L-1 for 324.754 nm, 249.215 nm and 224.426 nm, respectively and relative standard deviations (n = 12) were £ 2.7%. The proposed method was applied to water samples spiked with Cu and the results were in agreement at a 95% of confidence level (paired t-test) with those obtained by line-source flame atomic absorption spectrometry.

Cluster structure of atomic nuclei

Kirjallisuusarvostelu

Lujasta rakenneteräksestä tehdyn rakenteen vikasietoisuuden määritys

Tässä työssä tutkittiin Ruukin valmistamista lujista Optim 700 MC Plus sekä Optim 700 QL teräksistä tehtyjen hitsattujen palkkirakenteiden vikasietoisuutta sekä murtumiskäyttäytymistä laboratoriossa suoritettujen täyden mittakaavan kokeiden avulla. Koerakenteet suunniteltiin siten, että rakenteen kylmämuovauksen sekä hitsauksen vaikutukset yhdessä rakenteen geometrian vaikutuksen kanssa heikentävät rakenteen murtumissitkeyttä rakenteeseen tehdyn teräväkärkisen alkusärön tasossa. Suunnitellussa koesarjassa varioidaan testauslämpötilan lisäksi hitsauksen lämmöntuontia sekä koerakenteeseen tehtävän alkusärön kokoa. Tässä työssä tavoitteena oli yleisesti esittää menettely hitsatun säröllisen teräsrakenteen kestävyyden arviointia varten. Optim 700 MC Plus teräksestä tehdyn koerakenteen käyttäytymistä tutkittiin laskennallisesti murtumismekaniikan avulla. Laadittujen FEM - mallien avulla laskettiin rakenteen murtumisparametrien arvot kummallekin tutkittavalle teräkselle. Optim 700 MC Plus materiaalista valmistetuille koerakenteen säröalueen rakennedetaljia vastaavalle koekappaleille suoritettiin murtumissitkeyskokeita. Murtumissitkeyskokeista saatujen tulosten avulla pystyttiin kuvaamaan täyden mittakaavan koerakenteessa olevan särön murtumiskäyttäytymistä mitoitusmenetelmissä. Koerakenteelle laskettiin tässä työssä kriittisen särökoon ja sitä vastaavan kuorman arvot perustuen rakenteen oletettuun hauraaseen, epästabiiliin sitkeään sekä plastiseen murtumiskäyttäytymiseen. Tässä työssä testattiin molemmista tutkittavista materiaaleista valmistetut täyden mittakaavan koerakenteet -40 °C lämpötilassa. Molemmat testatut rakenteet käyttäytyvät mitattujen siirtymätulosten perusteella melko hauraasti. Optim 700 MC Plus materiaalille saatujen laskentatulosten voidaan todeta testatun koekappaleen perusteella soveltuvan hauraasti käyttäytyvän rakenteen mitoitukseen.

Atomic level phenomena on transition metal surfaces

In this study we discuss the atomic level phenomena on transition metal surfaces. Transition metals are widely used as catalysts in industry. Therefore, reactions occuring on transition metal surfaces have large industrial intrest. This study addresses problems in very small size and time scales, which is an important part in the overall understanding of these phenomena. The publications of this study can be roughly divided into two categories: The adsorption of an O2 molecule to a surface, and surface structures of preadsorbed atoms. These two categories complement each other, because in the realistic case there are always some preadsorbed atoms at the catalytically active surfaces. However, all transition metals have an active d-band, and this study is also a study of the in uence of the active d-band on other atoms. At the rst part of this study we discuss the adsorption and dissociation of an O2 molecule on a clean stepped palladium surface and a smooth palladium surface precovered with sulphur and oxygen atoms. We show how the reactivity of the surface against the oxygen molecule varies due to the geometry of the surface and preadsorbed atoms. We also show how the molecular orbitals of the oxygen molecule evolve when it approaches the di erent sites on the surface. In the second part we discuss the surface structures of transition metal surfaces. We study the structures that are intresting on account of the Rashba e ect and charge density waves. We also study the adsorption of suphur on a gold surface, and surface structures of it. In this study we use ab-initio based density functional theory methods to simulate the results. We also compare the results of our methods to the results obtained with the Low-Energy-Electron-Difraction method.

Field Weakening, Parameters and Operation Range of the Permanent Magnet Traction Motors

The main focus of this thesis is to define the field weakening point of permanent magnet synchronous machine with embedded magnets in traction applications. Along with the thesis a modelling program is made to help the designer to define the field weakening point in practical applications. The thesis utilizes the equations based on the current angle. These equations can be derived from the vector diagram of permanent magnet synchronous machine. The design parameters of the machine are: The maximum rotational speed, saliency ratio, maximum induced voltage and characteristic current. The main result of the thesis is finding out the rated rotational speed, from which the field weakening starts. The action of the machine is estimated at a wide speed range and the changes of machine parameters are examined.

Polymer surface modification by atomic layer deposition

Current industrial atomic layer deposition (ALD) processes are almost wholly confined to glass or silicon substrates. For many industrial applications, deposition on polymer substrates will be necessary. Current deposition processes are also typically carried out at temperatures which are too high for polymers. If deposition temperatures in ALD can be reduced to the level applicable for polymers, it will open new interesting areas and applications for polymeric materials. The properties of polymers can be improved for example by coatings with functional and protective properties. Although the ALD has shown its capability to operate at low temperatures suitable for polymer substrates, there are other issues related to process efficiency and characteristics of different polymers where new knowledge will assist in developing industrially conceivable ALD processes. Lower deposition temperature in ALD generally means longer process times to facilitate the self limiting film growth mode characteristic to ALD. To improve process efficiency more reactive precursors are introduced into the process. For example in ALD oxide processes these can be more reactive oxidizers, such as ozone and oxygen radicals, to substitute the more conventionally used water. Although replacing water in the low temperature ALD with ozone or plasma generated oxygen radicals will enable the process times to be shortened, they may have unwanted effects both on the film growth and structure, and in some cases can form detrimental process conditions for the polymer substrate. Plasma assistance is a very promising approach to improve the process efficiency. The actual design and placement of the plasma source will have an effect on film growth characteristics and film structure that may retard the process efficiency development. Due to the fact that the lifetime of the radicals is limited, it requires the placement of the plasma source near to the film growth region. Conversely this subjects the substrate to exposure byother plasma species and electromagnetic radiation which sets requirements for plasma conditions optimization. In this thesis ALD has been used to modify, activate and functionalize the polymer surfaces for further improvement of polymer performance subject to application. The issues in ALD on polymers, both in thermal and plasma-assisted ALD will be further discussed.

NON-DESTRUCTIVE ANALYSIS OF THE ROOT SYSTEM AND TREE GROWTH PARAMETERS

ABSTRACT The productivity of Eucalyptus at plantations is increasing and has undergone a variety of research studies. Most research is dealing with simple dendrometric variables like the DBH (diameter at breast height) and tree height, or more complex variables including crown parameters or variables concerning photosynthesis. The root systems, however, have not been well analyzed yet. The objective of the study was to analyze the root system with a non-destructive method and to evaluate possible correlations with dendrometric variables of the tree (DBH, height, crown expansion). A small experimental plantation with 39 even-aged, 6-year-old trees of Eucalyptus grandis x urophylla has been investigated within this study. The results of the study show the highest correlation of the root areas with the crown expansion. In general, the root area shows a significantly bigger expansion in the eucalypt plantation than the tree crown, with a more homogeneous development.

Effects of thermal environment and supplementation levels on the physiological parameters of moxotó goats in confined and semi-confined rising systems

The objective of this work was to determine the effect of environmental variables and supplementation levels on physiological parameters of Moxotó goats in confined and semi-confined rising systems, in the Brazilian semi-arid region. The semi-confined individuals were kept on a grass based diet during the day and arrested in the end of the afternoon. The confined animals were kept in a management center, receiving two diets composed by forage cactus and maniçoba hay into two different levels (0.5 and 1.5% of the body weight). Inside the management center and in the external environment the environmental comfort parameters were set high during the afternoon period characterizing a situation of thermal discomfort for the animals. During the morning the semi-confined animals presented an average respiratory frequency (69.5 mov min-1) and rectal temperature (39.5 ºC) higher than the confined ones (62.6 mov min-1 and 39.0 ºC, respectively). The confined and semi-confined animals were able to maintain their rectal temperature within normal limits, with increase in the cardiac beatings rate and respiratory frequency. The greater percentage of the used supplementations (1.5%) seemed to increase rectal temperature in the two studied rising systems.