Studies on the thermal decomposition behaviour, kinetics and electrical conductivity of the non-isothermal decomposition of pyridine mono carboxylic acids and some of their transition metal complexes

The thesis is divided into four chapters. They are: introduction, experimental, results and discussion about the free ligands and results and discussion about the complexes. The First Chapter, the introductory chapter, is a general introduction to the study of solid state reactions. The Second Chapter is devoted to the materials and experimental methods that have been used for carrying out tile experiments. TIle Third Chapter is concerned with the characterisations of free ligands (Picolinic acid, nicotinic acid, and isonicotinic acid) by using elemental analysis, IR spectra, X-ray diffraction, and mass spectra. Additionally, the thermal behaviour of free ligands in air has been studied by means of thermogravimetry (TG), derivative thermogravimetry (DTG), and differential scanning calorimetry (DSC) measurements. The behaviour of thermal decomposition of the three free ligands was not identical Finally, a computer program has been used for kinetic evaluation of non-isothermal differential scanning calorimetry data according to a composite and single heating rate methods in comparison with the methods due to Ozawa and Kissinger methods. The most probable reaction mechanism for the free ligands was the Avrami-Erofeev equation (A) that described the solid-state nucleation-growth mechanism. The activation parameters of the decomposition reaction for free ligands were calculated and the results of different methods of data analysis were compared and discussed. The Fourth Chapter, the final chapter, deals with the preparation of cobalt, nickel, and copper with mono-pyridine carboxylic acids in aqueous solution. The prepared complexes have been characterised by analyses, IR spectra, X-ray diffraction, magnetic moments, and electronic spectra. The stoichiometry of these compounds was ML2x(H20), (where M = metal ion, L = organic ligand and x = water molecule). The environments of cobalt, nickel, and copper nicotinates and the environments of cobalt and nickel picolinates were octahedral, whereas the environment of copper picolinate [Cu(PA)2] was tetragonal. However, the environments of cobalt, nickel, and copper isonicotinates were polymeric octahedral structures. The morphological changes that occurred throughout the decomposition were followed by SEM observation. TG, DTG, and DSC measurements have studied the thermal behaviour of the prepared complexes in air. During the degradation processes of the hydrated complexes, the crystallisation water molecules were lost in one or two steps. This was also followed by loss of organic ligands and the metal oxides remained. Comparison between the DTG temperatures of the first and second steps of the dehydration suggested that the water of crystallisation was more strongly bonded with anion in Ni(II) complexes than in the complexes of Co(II) and Cu(II). The intermediate products of decomposition were not identified. The most probable reaction mechanism for the prepared complexes was also Avrami-Erofeev equation (A) characteristic of solid-state nucleation-growth mechanism. The tempemture dependence of conductivity using direct current was determined for cobalt, nickel, Cl.nd copper isonicotinates. An activation energy (ΔΕ), the activation energy (ΔΕ ) were calculated.The ternperature and frequency dependence of conductivity, the frequency dependence of dielectric constant, and the dielectric loss for nickel isonicotinate were determined by using altemating current. The value of s paralneter and the value of'density of state [N(Ef)] were calculated. Keyword Thermal decomposition, kinetic, electrical conduclion, pyridine rnono~ carboxylic acid, cOlnplex, transition metal compJex.

(Table 4+5, Page 290) Distribution of Mn, Fe, Cu. Pb, Zn, Ni and Co in single manganese nodules

Chemical analyses of manganese nodules from the Central Pacific Basin show that their chemical composition varies regionally, although that of the associated sediments is markedly uniform throughout the basin. Mn content varies from 16 to 32% in average. Its higher value is generally found in nodules from siliceous clay and a few from deep-sea clay. Fe content tends to enrich in nodules from deep-sea clay area. Most manganese nodules, except those from deep-sea clay, are remarkably depleted in Fe compared with ones from the other Pacific regions. Mostly, Cu and Ni contents exceed 1% in nodules from siliceous clay, and decrease towards the northwest of the basin where deep-sea clay is distributed. The inter-element relationship between manganese nodules and associated sediments suggests that the mechanism of incorporation of major and minor elements in nodules is apparently different from that of the associated sediments. This finding seems to provide a new interpretation on the problem why manganese nodules having low accumulation rate are not buried by the associated sediments with greater sedimentation rate and then occur on sediment-seawater interface.

Annotated record and chemical composition of ferromanganese concretions and crusts sampled from the lakes and streams of Norway

The main objective of the project was to develop a geochemical method for exploration of ores associated with granitic rocks. Fe and Mn oxidates were sampled in streambeds and lakes from 129 localities in Southeastern Norway. 65 of these localities are situated in the northern Oslo Graben. The samples were examined mineralogically and chemically by a variety of methods. Geochemical maps of the element content in oxidates show regional distribution patterns for several elements. Sampling and analysis of oxidates can be used in exploration for mineralizations such as the Skrukkelia Mo-deposit in the northern Oslo Graben. New anomalies (especially for Zn and W) have been detected. Appendix I contains a description of samples, chemical and mineralogical determinations performed on the samples, backscattered electron image-, X-ray image- and scanning electron image pictures of the oxidate preparates. Appendix II contains spectral plots, point analysis with the microprobe, X-ray diffractograms, analytical results, correlation coefficient matrix, scatterplots, frequency distributions and information on data storage. Appendix III containS maps of the element content in oxidates.

Geochemical composition of nodules and crusts from the Indian Ocean recovered from R/V Marion Dufresne expeditions from 1977 until 1981

Following the launch of the "Marion Dufresne 1", first supply ship of the Terres Australes and Antarctiques Françaises and part time oceanographic vessel in the Indian Ocean, a new marine geology program was developped at the Laboratoire de Géologie, MNHN. The first oceanographic cruise of the "Marion Dufresne 1" started in 1973 in the Southwestern Indian Ocean (OSIRIS I cruise). Forty piston-cores recovered nearly 200 m of sediments consisting in the first of the 450 cores of the Indian Ocean collection now deposited at the Museum. L. Leclaire being Director from 1980 to 1991, a multidisciplinary team (including sedimentologists and micropaleontologists) was involved in many oceanographic cruises in the Indian Ocean. Marine sedimentology was developped during annual cruises programs in collaboration with geophysicists, geochemists, and biologists. In 1995, the "Marion Dufresne 2" replaced the initial "Marion Dufresne 1".

(Table 5, page 626), Tin and main metal elements composition of ferromanganese concretions (acid-soluble fractions)

Concentrations of tin in sea water decreased from estuarine and shelf (0.02-0.04 µg/kg) to surface Atlantic waters (0.009 µg/kg). Mean contents (ppm) in other materials included: ultramafic rocks, 0.8; basalts, 1.7; silicic rocks, 2.5; red clays, 3.4; amphibolites, 1.2. Oceanic ferromanganese deposits contained from 0.2 to 5.8 ppm; tin and cobalt contents were correlated.

Geochemistry and descriptions of manganese nodules and crusts retrieved from the open ocean

The book is a compilation of all available data at the time of publication (1965) on the subject of marine minerals together with the author's original ideas regarding their exploitation. It is one of the most significant publications on ocean resources. It is particularly focused on manganese deposits, their description, sedimentary setting, formation and geochemistry.

(Table 1, Page 1046-1047) Chemical composition of iron-manganese concretions from the Indian Ocean recovered by the R/V Vityaz and the R/V Ob

The data given in this and previous communications is insufficient to assess the quantitative role of these supplementary sources in the Indian Ocean, but they do not rule out their local significance. Elucidation of this problem requires further data on the characteristics of the composition and structure of nodules in various different metallogenic regions of the ocean floor. A study of the distribution of ore elements in nodules both depthwise and over the area of the floor together with compilation of the first schematic maps based on the results of analyses of samples from 54 stations) enables us to give a more precise empirical relation between the Mn, Fe, Ni, Cu, and Co contents in Indian Ocean nodules, the manganese ratio and the values of the oxidation potential, which vary regularly with depth. This in turn also enables us to confirm that formation of nodules completes the prolonged process of deposition of ore components from ocean waters, and the complex physico-chemical transformations of sediments in the bottom layer. Microprobe investigation of ore rinds revealed the nonuniform distribution of a num¬ber of elements within them, owing to the capacity of particles of hydrated oxides of manganese and iron to adsorb various elements. High concentration of individual elements is correlated with local sectors of the ore rinds, in which the presence of todorokite, in particular, has been noted. The appearance of this mineral apparently requires elevated Ca, Mg, Na, and K concentrations, because the stable crystalline phase of this specific mineral form of the psilomelane group may be formed when these cations are incorporated into a lattice of the delta-MnO2 type.

(Table 2, Page 252) Average chemical composition of 11 manganese nodules and crust from the Pacific Ocean

The ability of the hydrated oxides of manganese and iron to adsorb ions from solution (scavenging) is considered in relation to some problems in marine geology, chemistry, and biology. In the ferruginous sediments of the Pacific Ocean, iron oxides are accompanied by titanium, cobalt, and zirconium in amounts proportional to the iron content. Similarly, copper and nickel are linearly related to the manganese content. These observations are explained on the basis of scavenging. An electrochemical theory for the formation of manganese nodules is presented. Marine sediments are classified on the basis of the geosphere in which the solid phases originate. The distribution of certain ionic species in sea water between the solid and aqueous phases is considered on the basis of scavenging and co-ordination compound theory. The concentration of minor elements by members of the marine biosphere is explained either by the direct uptake of the element or by the uptake of iron or manganese oxides with the accompanying scavenged element.

(Table, page 351-359) Chemical composition of manganese nodules and crusts from the Pacific and Indian Ocean

Chemical and mineralogical analyses of manganese nodules from a large number of widely spaced localities in the Pacific and Indian Oceans have shown that their mineralogy and chemical composition varies both areally and with depth of formation. This is considered to result from a number of factors, important among which are: (a) their proximity to continental or volcanic sources of elements; (b) the chemical environment of deposition, including the degree of oxygenation; and (c) local factors such as the upward migration of reduced manganese in sediments from certain areas. Sub-surface nodules appear to share the chemical characteristics of their surface counterparts, especially those from volcanic areas where sub-surface sources of elements are probably important.

Lithological and chemical composition, stages of sediment accumulation, and sedimentation rates in Core PSh24-2537, West Gotland Basin, Baltic Sea

We studied the grain-size, mineral and chemical compositions, physical properties, radiocarbon age, spore-pollen spectra, and diatom composition in sediments from Core PSh24-2537 sampled in the West Gotland Basin. Four lithological-stratigraphic units were distinguished: varved clays of the Baltic Ice Lake, black and black-gray (sulfide) clays of the Yoldian Sea, gray clays of Ancylus Lake, and greenish-gray sapropel-like littorine and post-littorine silts of the marine stage of Holocene. These units differ from each other both in their matter composition and in plant remains. In the littorine silts organic carbon concentra¬tion reached from 1.5 to 10.35%. Conditions of sediment accumulation and the stages of evolution of the West Gotland Basin over the post-glacial time are characterized.

Chemical composition of hydrothermal carbonates and barites from the Deryugin Basin, Sea of Okhotsk

Data on hydrothermal activity in the Deryugin Basin (Sea of Okhotsk) are reviewed. Barites and carbonates found in sediment cores sampled at feet of hydrothermal mounds were subdivided into recycled and authigenic types. Recycled minerals were represented by crystals and aggregations of travertine-like barite and fragments of barite and carbonate tubes. Authigenic formations included: (1) carbonate nodules; (2) barite micronodules; (3) transparent colorless barite that generated numerous small nests and filled cavities in sediments; (4) yellow barite formed thin (0.5 mm) veins; and (5) white barite cemented small aggregations of coarse-grained sediments. A detailed examination of formation processes of authigenic minerals in the bottom sediment cores allowed to conclude that, there, hydrothermal activity is still going on today. This was confirmed by high methane concentration in near-bottom water above a field of hydrothermal barite minerals.

Basalt analyses from different DSDP Holes in the Mozambique Basin and Ridge and from the Southwest Indian Ridge

Basalts from DSDP Sites 248, 249, 250 and 251 in the southwestern Indian Ocean formed in a complex tectonic region affected by the separation of Africa and South America. The different ages and variable geochemical features of these DSDP basalts probably reflect this tectonic complexity. For example, Site 251 on the flanks of the Southwest Indian Ridge is represented by normal MORB which probably originated at the Southwest Indian Ridge. Site 250 in the Mozambique Basin includes an older incompatible- element enriched unit which may represent basalt associated with the Prince Edward Fracture Zone; the upper unit is normal MORB. Basalts at Site 248 also in the Mozambique Basin are geochemically very unlike MORB and have strong continental affinities; they are also comparable in age to some of the continental Karroo basalts. They appear to be related to a subcontinental mantle source or to contamination by continental basement associated with the tectonic elevation of the Mozambique Ridge. Basalts from Site 249 on the Mozambique Ridge are relatively weathered but appear to be normal MORB. Their age, location, and composition are consistent with their origin at an early Cretaceous rift which has been postulated to have separated the Falkland Plateau from the Mozambique Ridge.

Annotated record and chemical composition of Mn deposits from R/V Mahi Cruise Abyssal Hills 69 stations

A University of Hawaii oceanographic cruise, Abyssal Hills 69, with the R/V Mahi, was carried out to study the association of manganese nodules with an abyssal hill. Manganese nodules from three dredge hauls on an abyssal hill located at 36°W and 157°W exhibited differences in morphology and composition between stations only three miles apart. The morphology of the nodules suggests that nodules from a single site have similar morphologies because they began growth at the same time, probably because of a volcanic event. Differences in morphology between stations indicate a local supply of elements. Atomic absorption analysis for manganese, iron, cobalt, nickel, and copper revealed that nodules nearest to a probable fault line and source of volcanism have a, lower manganese to iron ratio than nodules farther removed. This finding supports the theory that volcanism contributes to the formation of some nodules. Additional evidence showing association with volcanism consists of volcanic nuclei in nodules, crusts formed on layers of volcanic ash, and basalt encrusted to various degrees. The variation in cobalt, nickel, and copper contents Gt the nodules from a single dredge is two-to threefold, but iron content is more uniiorm. Four of the six cores from the area increased in manganese concentration with depth, suggesting that diffusion is concentrating manganese in the upper zone of the sediments or in nodules. The author concludes that volcanism is contributing to the formation of nodules by supplying nuclei and transition elements, but is not necessary for the formation of manganese nodules.

Description, geochemistry and growth rate of buried nodules from the Central Indian Basin

Buried nodules from siliceous sediments in the central Indian Basin are morphologically variable and mineralogically consist of d-MnO2 and incipient todorokite. Compositionally they are weakly diagenetic. The sediment coarse fractions (>63 µm) at different depths show variable abundances of micronodules, volcanic glass shards and biodebris. Dissolution of biodebris increases and abundance of micronodules decreases with increasing depth. Enrichment in Mn, Fe, Cu, Ni, Co, together with a decrease in organic carbon in the sediment column, may result from diagenetic metal remobilization. Diagenetically remobilized trace metals might have been utilized for the growth of micronodules over the buried nodules.