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  • kinetics  (727)
  • 04. Solid Earth::04.08. Volcanology::04.08.03. Magmas
  • Tsunami
  • Springer  (749)
  • Nature Publishing Group  (4)
  • American Meteorological Society (AMS)
  • 1
    Publication Date: 2017-04-04
    Description: In this paper, we describe the 1809 eruption of Mt. Etna, Italy, which represents one historical rare case in which it is possible to observe details of the internal structure of the feeder system. This is possible thanks to the presence of two large pit craters located in the middle of the eruptive fracture field that allow studying a section of the shallow feeder system. Along the walls of one of these craters, we analysed well-exposed cross sections of the uppermost 15–20 m of the feeder system and related volcanic products. Here, we describe the structure, morphology and lithology of this portion of the 1809 feeder system, including the host rock which conditioned the propagation of the dyke, and compare the results with other recent eruptions. Finally, we propose the dynamic model of the magma behaviour inside a laterally-propagating feeder dyke, demonstrating how this dynamic triggered important changes in the eruptive style (from effusive/Strombolian to phreatomagmatic) during the same eruption. Our results are also useful for hazard assessment related to the development of flank eruptions, potentially the most hazardous type of eruption from basaltic volcanoes in densely urbanized areas, such as Mt. Etna.
    Description: Published
    Description: 1-11
    Description: 2T. Tettonica attiva
    Description: 2V. Dinamiche di unrest e scenari pre-eruttivi
    Description: 3V. Dinamiche e scenari eruttivi
    Description: 4V. Vulcani e ambiente
    Description: 6A. Monitoraggio ambientale, sicurezza e territorio
    Description: N/A or not JCR
    Description: open
    Keywords: feeder dyke ; basaltic volcanoes ; flank eruptions ; Etna ; volcanic hazards ; sill ; volcanic rift ; 04. Solid Earth::04.04. Geology::04.04.09. Structural geology ; 04. Solid Earth::04.07. Tectonophysics::04.07.07. Tectonics ; 04. Solid Earth::04.08. Volcanology::04.08.99. General or miscellaneous ; 04. Solid Earth::04.08. Volcanology::04.08.03. Magmas ; 04. Solid Earth::04.08. Volcanology::04.08.04. Thermodynamics ; 04. Solid Earth::04.08. Volcanology::04.08.05. Volcanic rocks ; 04. Solid Earth::04.08. Volcanology::04.08.08. Volcanic risk ; 05. General::05.02. Data dissemination::05.02.03. Volcanic eruptions
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
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  • 2
    Publication Date: 2017-04-04
    Description: The 2011 Tohoku-oki (Mw 9.1) earthquake is so far the best-observed megathrust rupture, which allowed the collection of unprecedented offshore data. The joint inversion of tsunami waveforms (DART buoys, bottom pressure sensors, coastal wave gauges, and GPS-buoys) and static geodetic data (onshore GPS, seafloor displacements obtained by a GPS/acoustic combination technique), allows us to retrieve the slip distribution on a non-planar fault. We show that the inclusion of near-source data is necessary to image the details of slip pattern (maximum slip ,48 m, up to ,35 m close to the Japan trench), which generated the large and shallow seafloor coseismic deformations and the devastating inundation of the Japanese coast. We investigate the relation between the spatial distribution of previously inferred interseismic coupling and coseismic slip and we highlight the importance of seafloor geodetic measurements to constrain the interseismic coupling, which is one of the key-elements for long-term earthquake and tsunami hazard assessment.
    Description: Published
    Description: 385
    Description: 3.1. Fisica dei terremoti
    Description: N/A or not JCR
    Description: restricted
    Keywords: Tohoku ; Subduction ; Tsunami ; Inverse problem ; 04. Solid Earth::04.06. Seismology::04.06.03. Earthquake source and dynamics ; 04. Solid Earth::04.07. Tectonophysics::04.07.06. Subduction related processes
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 3
    Publication Date: 2017-04-04
    Description: In recent decades, geophysical investigations have detected wide magma reservoirs beneath quiescent calderas. However, the discovery of partially melted horizons inside the crust is not sufficient to put constraints on capability of reservoirs to supply cataclysmic eruptions, which strictly depends on the chemical-physical properties of magmas (composition, viscosity, gas content etc.), and thus on their differentiation histories. In this study, by using geochemical, isotopic and textural records of rocks erupted from the high-risk Campi Flegrei caldera, we show that the alkaline magmas have evolved toward a critical state of explosive behaviour over a time span shorter than the repose time of most volcanic systems and that these magmas have risen rapidly toward the surface. Moreover, similar results on the depth and timescale of magma storage were previously obtained for the neighbouring Somma-Vesuvius volcano. This consistency suggests that there might be a unique long-lived magma pool beneath the whole Neapolitan area.
    Description: Published
    Description: article 712
    Description: 2.3. TTC - Laboratori di chimica e fisica delle rocce
    Description: 3.5. Geologia e storia dei vulcani ed evoluzione dei magmi
    Description: 3.6. Fisica del vulcanismo
    Description: 4.3. TTC - Scenari di pericolosità vulcanica
    Description: N/A or not JCR
    Description: open
    Keywords: magma ; campi flegrei caldera ; 04. Solid Earth::04.04. Geology::04.04.05. Mineralogy and petrology ; 04. Solid Earth::04.08. Volcanology::04.08.03. Magmas ; 04. Solid Earth::04.08. Volcanology::04.08.05. Volcanic rocks ; 04. Solid Earth::04.08. Volcanology::04.08.08. Volcanic risk
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 4
    Publication Date: 2022-05-25
    Description: © The Author(s), 2010. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Natural Hazards 63 (2012): 51-84, doi:10.1007/s11069-010-9622-6.
    Description: Waters from the Atlantic Ocean washed southward across parts of Anegada, east-northeast of Puerto Rico, during a singular event a few centuries ago. The overwash, after crossing a fringing coral reef and 1.5 km of shallow subtidal flats, cut dozens of breaches through sandy beach ridges, deposited a sheet of sand and shell capped with lime mud, and created inland fields of cobbles and boulders. Most of the breaches extend tens to hundreds of meters perpendicular to a 2-km stretch of Anegada’s windward shore. Remnants of the breached ridges stand 3 m above modern sea level, and ridges seaward of the breaches rise 2.2–3.0 m high. The overwash probably exceeded those heights when cutting the breaches by overtopping and incision of the beach ridges. Much of the sand-and-shell sheet contains pink bioclastic sand that resembles, in grain size and composition, the sand of the breached ridges. This sand extends as much as 1.5 km to the south of the breached ridges. It tapers southward from a maximum thickness of 40 cm, decreases in estimated mean grain size from medium sand to very fine sand, and contains mud laminae in the south. The sand-and-shell sheet also contains mollusks—cerithid gastropods and the bivalve Anomalocardia—and angular limestone granules and pebbles. The mollusk shells and the lime-mud cap were probably derived from a marine pond that occupied much of Anegada’s interior at the time of overwash. The boulders and cobbles, nearly all composed of limestone, form fields that extend many tens of meters generally southward from limestone outcrops as much as 0.8 km from the nearest shore. Soon after the inferred overwash, the marine pond was replaced by hypersaline ponds that produce microbial mats and evaporite crusts. This environmental change, which has yet to be reversed, required restriction of a former inlet or inlets, the location of which was probably on the island’s south (lee) side. The inferred overwash may have caused restriction directly by washing sand into former inlets, or indirectly by reducing the tidal prism or supplying sand to post-overwash currents and waves. The overwash happened after A.D. 1650 if coeval with radiocarbon-dated leaves in the mud cap, and it probably happened before human settlement in the last decades of the 1700s. A prior overwash event is implied by an inland set of breaches. Hypothetically, the overwash in 1650–1800 resulted from the Antilles tsunami of 1690, the transatlantic Lisbon tsunami of 1755, a local tsunami not previously documented, or a storm whose effects exceeded those of Hurricane Donna, which was probably at category 3 as its eye passed 15 km to Anegada’s south in 1960.
    Description: The work was supported in part by the Nuclear Regulatory Commission under its project N6480, a tsunami-hazard assessment for the eastern United States.
    Keywords: Tsunami ; Stratigraphy ; Caribbean
    Repository Name: Woods Hole Open Access Server
    Type: Article
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  • 5
    Publication Date: 2017-04-04
    Description: The MW 8.8 mega-thrust earthquake and tsunami that occurred on February 27, 2010, offshore Maule region, Chile, was not unexpected. A clearly identified seismic gap existed in an area where tectonic loading has been accumulating since the great 1835 earthquake experienced and described by Darwin during the voyage of the Beagle. Here we jointly invert tsunami and geodetic data (InSAR, GPS, land-level changes), to derive a robust model for the co-seismic slip distribution and induced co-seismic stress changes, and compare them to past earthquakes and the pre-seismic locking distribution. We aim to assess if the Maule earthquake has filled the Darwin gap, decreasing the probability of a future shock . We find that the main slip patch is located to the north of the gap, overlapping the rupture zone of the MW 8.0 1928 earthquake, and that a secondary concentration of slip occurred to the south; the Darwin gap was only partially filled and a zone of high pre-seismic locking remains unbroken. This observation is not consistent with the assumption that distributions of seismic rupture might be correlated with pre-seismic locking, potentially allowing the anticipation of slip distributions in seismic gaps. Moreover, increased stress on this unbroken patch might have increased the probability of another major to great earthquake there in the near future.
    Description: Published
    Description: 173-177
    Description: 3.1. Fisica dei terremoti
    Description: 4.2. TTC - Modelli per la stima della pericolosità sismica a scala nazionale
    Description: JCR Journal
    Description: restricted
    Keywords: Source process ; Chile ; Tsunami ; Joint Inversion ; Seismic Gap ; 04. Solid Earth::04.06. Seismology::04.06.99. General or miscellaneous ; 04. Solid Earth::04.07. Tectonophysics::04.07.05. Stress ; 04. Solid Earth::04.07. Tectonophysics::04.07.06. Subduction related processes ; 05. General::05.01. Computational geophysics::05.01.03. Inverse methods
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 6
    Publication Date: 2017-04-04
    Description: During its 1800-year-long persistent activity the Stromboli volcano has erupted a highly porphyritic (HP) volatile-poor scoriaceous magma and a low porphyritic (LP) volatile-rich pumiceous magma. The HP magma is erupted during normal Strombolian explosions and lava effusions, while the LP one is related to more energetic paroxysms. During the March–April 2003 explosive activity, Stromboli ejected two typologies of juvenile glassy ashes, namely highly vesicular LP shards and volatile-poor HP shards. Their textural and in situ chemical characteristics are used to unravel mutual relationships between HP and LP magmas, as well as magma dynamics within the shallow plumbing system. The mantle-normalized trace element patterns of both ash types show the typical arc-lava pattern; however, HP glasses possess incompatible element concentrations higher than LP glasses, along with Sr and Eu negative anomalies. HP shards are generally characterized by higher Li contents (to ~20 ppm) and lower δ7Li values (+1.2 to −3.8‰) with respect to LP shards (Li contents of 7–14 ppm and δ7Li ranging between +4.6 and +0.9‰). Fractional crystallization models based on major and trace element compositions, combined with a degassing model based on open-system Rayleigh distillation and on the assumption that melt/fluidDLi 〉 1, show that abundant (~30%) plagioclase precipitation and variable degrees of degassing can lead the more primitive LP magma to evolve toward a differentiated (isotopically lighter) HP magma ponding in the upper conduit and undergoing slow continuous degassing-induced crystallization. This study also evidences that in March 2003 Stromboli volcano poured out a small early volume of LP magma that traveled slower within the conduit with respect to later and larger volumes of fast ascending LP magma erupted during the April 5 paroxysm. The different ascent rates and cooling rates of the two LP magma batches (i.e., pre- and post-paroxysm) resulted in small, but detectable, differences in their chemical signatures. Finally, this study highlights the high potential of in situ investigations of juvenile glassy ashes in petrologic and geochemical monitoring the volcanic activity and of Li isotopes as tracers of degassing processes within the shallow plumbing system.
    Description: Published
    Description: 541-561
    Description: 1.5. TTC - Sorveglianza dell'attività eruttiva dei vulcani
    Description: 2.3. TTC - Laboratori di chimica e fisica delle rocce
    Description: 3.5. Geologia e storia dei vulcani ed evoluzione dei magmi
    Description: JCR Journal
    Description: reserved
    Keywords: Stromboli ; Volcanic ash ; Lithium isotopes ; Degassing-induced crystallization ; Petrologic monitoring ; 04. Solid Earth::04.04. Geology::04.04.05. Mineralogy and petrology ; 04. Solid Earth::04.08. Volcanology::04.08.03. Magmas ; 04. Solid Earth::04.08. Volcanology::04.08.06. Volcano monitoring
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  • 7
    Publication Date: 2017-04-04
    Description: The AND-2A drillcore (Antarctic Drilling Program—ANDRILL) was successfully completed in late 2007 on the Antarctic continental margin (Southern McMurdo Sound, Ross Sea) with the aim of tracking ice proximal to shallow marine environmental fluctuations and to document the 20-Ma evolution of the Erebus Volcanic Province. Lava clasts and tephra layers from the AND-2A drillcore were investigated from a petrographic and stratigraphic point of view and analyzed by the 40Ar–39Ar laser technique in order to constrain the age model of the core and to gain information on the style and nature of sediment deposition in the Victoria Land Basin since Early Miocene. Ten out of 17 samples yielded statistically robust 40Ar–39Ar ages, indicating that the AND-2A drillcore recovered ≤230 m of Middle Miocene (∼128–358 m below sea floor, ∼11.5–16.0 Ma) and 〉780 m of Early Miocene (∼358–1093 m below sea floor, ∼16.0–20.1 Ma). Results also highlight a nearly continuous stratigraphic record from at least 358 m below sea floor down hole, characterized by a mean sedimentation rate of ∼19 cm/ka, possible oscillations of no more than a few hundreds of ka and a break within ∼17.5–18.1 Ma. Comparison with available data from volcanic deposits on land, suggests that volcanic rocks within the AND-2A core were supplied from the south, possibly with source areas closer to the drill site for the upper core levels, and from 358 m below sea floor down hole, with the “proto-Mount Morning” as the main source.
    Description: Published
    Description: 487-505
    Description: 2.3. TTC - Laboratori di chimica e fisica delle rocce
    Description: 3.5. Geologia e storia dei vulcani ed evoluzione dei magmi
    Description: JCR Journal
    Description: reserved
    Keywords: ANDRILL SMS ; 40Ar–39Ar geochronology ; Erebus volcanic province ; McMurdo Sound ; Lava clasts ; Sedimentation rate ; Tephra layers ; Victoria Land Basin ; 04. Solid Earth::04.04. Geology::04.04.02. Geochronology ; 04. Solid Earth::04.08. Volcanology::04.08.03. Magmas ; 04. Solid Earth::04.08. Volcanology::04.08.05. Volcanic rocks
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 8
    Publication Date: 2017-04-04
    Description: We describe the mineralogy, geochemistry, and mesomicrostructure of fresh subvolcanic blocks erupted during the 5 April 2003 paroxysm of Stromboli (Aeolian Islands, Italy). These blocks represent ∼50 vol.% of the total erupted ejecta and consist of fine- to medium-grained basaltic lithotypes ranging from relatively homogeneous dolerites to strongly or poorly welded magmatic breccias. The breccia components are represented by angular fragments of dolerites entrapped in a matrix of vesiculated (lava-like to scoriae) crystal-rich (CR) basalt. All of the studied blocks are cognates with the CR basalt of the normal Strombolian activity or lavas and they are often coated by a few-centimeter thick layer of crystal-poor (CP) basaltic pumice erupted during the paroxysm. We suggest that they result from the rapid increase of pressure and related subvolcanic rock failure that occurred shortly before the 5 April 2003 explosion, when the uppermost portion of the edifice inflated and suffered brecciation as the result of the sudden rise of the gas-rich CP basalt that triggered the eruption. Dolerites and magmatic matrix of the breccias show major and trace element compositions that match those of the CR basalts erupted during normal Strombolian activity and effusive events at Stromboli volcano. Dolerites consist of (a) phenocrysts normally found in the CR basalts and (b) late-stage magmatic minerals such as sanidine, An60-28 plagioclase, Fe–Mn-rich olivines (Fo68-48), phlogopite, apatite, and opaque mineral pairs (magnetite and ilmenite), most of which are never found both in lava flows and scoriae erupted during the persistent explosive activity that characterizes typical Strombolian behavior. Subvolcanic crystallization of the Stromboli CR magma, leading to slowly cooled equivalents of basalts, could result from transient drainage of the magma from the summit craters to lower levels. Fingering and engulfing of the material that collapsed from the summit crater floor into the shallow basaltic system during the late evening of 28 December 2002 coupled with the short break in the summit persistent explosions between December 2002 and March 2003 permitted the CR magma pockets to solidify as dolerites, which were confined to the uppermost portion of the system and thus not involved in the ongoing flank effusive activity. Crystal size distribution of the basaltic blocks and crystallization of the finer-grained (〈0.1 mm) mafic minerals of the dolerites over a time interval of ∼100 days closely agrees with the above interpretation. Vesicle filling (miarolitic cavities) locally found in some dolerites, with minerals deposited as vapor-phase crystallization is a result of continuous gas percolation through the rocks of the uppermost portion of the volcanic system. Poorly welded magmatic breccias formed during syn-eruptive processes of 5 April 2003, when the paroxysm strongly shattered the shallow subvolcanic system and many dolerite fragments were entrapped in the CR magma. In contrast, the high degree of welding between the dolerite clasts and the CR basaltic matrix in the strongly welded magmatic breccias provides a snapshot of subvolcanic intrusions of the CR basalt into the dolerite when, after a 2-month break in activity, CR magmas started to rise again to the summit craters. Blocks similar to these subvolcanic ejecta of 5 April 2003 were also erupted during previous paroxysms (e.g., 1930) suggesting that changes in the usual Strombolian activity (e.g., short breaks in the persistent mild explosions and/or flank effusive activity) lead to transient crystallization of dolerites in the shallow plumbing system.
    Description: Published
    Description: 795-813
    Description: 3.5. Geologia e storia dei vulcani ed evoluzione dei magmi
    Description: JCR Journal
    Description: reserved
    Keywords: Basalt ; Subvolcanic crystallization ; Dolerite ; Magmatic breccia ; Stromboli ; 04. Solid Earth::04.04. Geology::04.04.05. Mineralogy and petrology ; 04. Solid Earth::04.08. Volcanology::04.08.03. Magmas
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 9
    Publication Date: 2017-04-04
    Description: New Sr and Nd isotope data for whole rocks, glasses and minerals are combined to reconstruct the nature and origin of mixing end-members of the 200 km3 trachytic to phonolitic Campanian Ignimbrite (Campi Flegrei, Italy) magmatic system. The least-evolved magmatic end-member shows equilibrium between host glass and the majority of the phenocrysts and is less radiogenic in Sr and Nd than the most-evolved magma. On the contrary, only the Fe-rich pyroxene from the most-evolved erupted magma is in equilibrium with the matrix glass, while all other minerals are in isotopic disequilibrium. These magmas mixed prior to and during the Campanian Ignimbrite eruption and minerals were freely exchanged between the magma batches. Combining the results of the geochemical investigations on magma end-members with geophysical and geological data, we develop the following scenario. In stage 1, a parental, less differentiated magma rose into the middle crust, and evolved through combined crustal assimilation and crystal fractionation. In stage 2, the differentiated magma rose to shallower depth, fed the pre-Campanian Ignimbrite activity and evolved by further open-system processes into the most-evolved and most-radiogenic Campanian Ignimbrite end-member magma. In stage 3, new trachytic magma, isotopically distinct from the pre-Campanian Ignimbrite magmas, rose from ca. 6 km to shallower depth, recharged the most-evolved pre-Campanian Ignimbrite magma chamber, and formed the large and stratified Campanian Ignimbrite magmatic system. During the course of the Campanian Ignimbrite eruption, the two layers were tapped separately and/or simultaneously, and gave rise to the range of chemical and isotopic values displayed by the Campanian Ignimbrite pumices, glasses and minerals.
    Description: Published
    Description: 285-300
    Description: 2.3. TTC - Laboratori di chimica e fisica delle rocce
    Description: 3.5. Geologia e storia dei vulcani ed evoluzione dei magmi
    Description: JCR Journal
    Description: reserved
    Keywords: Campanian Ignimbrite ; Radiogenic isotopes ; Mixing process ; 04. Solid Earth::04.08. Volcanology::04.08.03. Magmas ; 04. Solid Earth::04.08. Volcanology::04.08.05. Volcanic rocks
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 10
    Publication Date: 2017-04-04
    Description: Following the 2001 and 2002–2003 flank eruptions, activity resumed at Mt. Etna on 7 September 2004 and lasted for about 6 months. This paper presents new petrographic, major and trace element, and Sr–Nd isotope data from sequential samples collected during the entire 2004–2005 eruption. The progressive change of lava composition allowed defining three phases that correspond to different processes controlling magma dynamics inside the central volcano conduits. The compositional variability of products erupted up to 24 September is well reproduced by a fractional crystallization model that involves magma already stored at shallow depth since the 2002–2003 eruption. The progressive mixing of this magma with a distinct new one rising within the central conduits is clearly revealed by the composition of the products erupted from 24 September to 15 October. After 15 October, the contribution from the new magma gradually becomes predominant, and the efficiency of the mixing process ensures the emission of homogeneous products up to the end of the eruption. Our results give insights into the complex conditions of magma storage and evolution in the shallow plumbing system of Mt. Etna during a flank eruption. Furthermore, they confirm that the 2004–2005 activity at Etna was triggered by regional movements of the eastern flank of the volcano. They caused the opening of a complex fracture zone extending ESE which drained a magma stored at shallow depth since the 2002–2003 eruption. This process favored the ascent of a different magma in the central conduits, which began to be erupted on 24 September without any significant change in eruptive style, deformation, and seismicity until the end of eruption.
    Description: Published
    Description: 781–793
    Description: 2.3. TTC - Laboratori di chimica e fisica delle rocce
    Description: JCR Journal
    Description: reserved
    Keywords: Geochemistry ; Isotopic compositions ; Magma feeding system ; Magma mixing ; Mt. Etna ; 04. Solid Earth::04.08. Volcanology::04.08.03. Magmas ; 04. Solid Earth::04.08. Volcanology::04.08.05. Volcanic rocks
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 11
    Publication Date: 2017-04-04
    Description: A series of experiments created melt inclusions in plagioclase and pyroxene crystals grown from a basaltic melt at 1,150 C, 1.0 GPa to investigate diffusive fractionation during melt inclusion formation; additionally, P diffusion in a basaltic melt was measured at 1.0 GPa. Melt inclusions and melts within a few 100 microns of plagioclase– melt interfaces were analyzed for comparison with melt compositions far from the crystals. Melt inclusions and melt compositions in the boundary layer close to the crystal–melt interface were similar, but both differ significantly in incompatible element concentrations from melt found greater than approximately 200 microns away from the crystals. The compositional profiles of S, Cl, P, Fe, and Al in the boundary layers were successfully reproduced by a two-step model of rapid crystal growth followed by diffusive relaxation toward equilibrium after termination of crystal growth. Applying this model to investigate possible incompatible element enrichment in natural melt inclusions demonstrated that at growth rates high enough to create the conditions for melt inclusion formation, *10-9–10-8 m s-1, the concentration of water in the boundary layer near the crystal was similar to that of the bulk melt because of its high diffusion coefficient, but sulfur, with a diffusivity similar to major elements and CO2, was somewhat enriched in the boundary layer melt, and phosphorus, with its low diffusion coefficient similar to other high-field strength elements and rare earth elements, was significantly enriched. Thus, the concentrations of sulfur and phosphorus in melt inclusions may over-estimate their values in the bulk melt, and other elements with similar diffusion coefficients may also be enriched in melt inclusions relative to the bulk melt.
    Description: Natural Sciences and Engineering Research Council of Canada Discovery grant; Istituto Nazionale di Geofisica and Vulcanologia, Italy
    Description: Published
    Description: 377-395
    Description: 2.3. TTC - Laboratori di chimica e fisica delle rocce
    Description: JCR Journal
    Description: reserved
    Keywords: Melt inclusions ; Phosphorus diffusion ; Crystal growth ; Diffusive Fractionation ; 04. Solid Earth::04.08. Volcanology::04.08.03. Magmas
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 12
    Publication Date: 2017-04-04
    Description: We have characterized pumice products belonging to the climactic phase of the 800-year-b.p. Quilotoa eruption. Bulk rock compositions, petrography, mineral, and glass chemistry and textural investigations were performed on the three end-member pumice types, namely white, gray, and mingled pumices. All the investigated pumice clasts are dacites characterized by the same bulk rock composition and mineralogical assemblage, but glass compositions and bulk textures change according to different pumice types. White pumice has higher crystallinity (~48 wt%), abundant euhedral pheno/microphenocrysts, no groundmass microlites, the most evolved glass compositions (7478 wt% SiO2), and heterogeneous vesicle populations marked by deformed and highly coalesced vesicles with thin walls. Gray pumice exhibits lower crystallinity (2936 wt%), abundant broken and/or resorbed crystals, ubiquitous groundmass phenocryst fragments and microlites, the widest range of glass compositions (6978 wt% SiO2), and quite homogeneous poorly deformed and coalesced vesicles with thicker walls. Mingled pumices are characterized by the alternation of bands or patches with white and gray pumice compositional and textural characteristics. We attribute heterogeneities in glass compositions and crystal and vesicle textures to processes occurring within volcanic conduits as magma is ascending to the surface. In particular, the above observations and results are consistent with an origin of a gray magma by heating of the original white magma in a strongly sheared region of the conduit because of a mechanism of viscous dissipation and crystal grinding and resorption at the conduit walls. The less viscous gray magma, therefore, would enable the onset and preservation of a high mass flux of the eruption otherwise difficult to explain for highly viscous crystal-rich dacitic magmas.
    Description: Published
    Description: 307-321
    Description: partially_open
    Keywords: Plinian eruption ; Crystal-rich magma ; Crystal grinding ; Pumice types ; Viscous dissipation ; 04. Solid Earth::04.08. Volcanology::04.08.03. Magmas ; 05. General::05.02. Data dissemination::05.02.03. Volcanic eruptions
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 13
    Electronic Resource
    Electronic Resource
    Springer
    Adsorption 6 (2000), S. 137-147 
    ISSN: 1572-8757
    Keywords: adsorption ; kinetics ; linear driving force model ; process design
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract The Linear Driving Force (LDF) model for gas adsorption kinetics is frequently and successfully used for analysis of adsorption column dynamic data and for adsorptive process designs because it is simple, analytic, and physically consistent. Yet, there is a substantial difference in the characteristics of isothermal batch uptake curves on adsorbent particles by the LDF and the more rigorous Fickian Diffusion (FD) model. It is demonstrated by using simple model systems that the characteristics of the adsorption kinetics at the single pore or the adsorbent particle level are lost in (a) evaluating overall uptake on a heterogeneous porous solid, (b) calculating breakthrough curves from a packed adsorbent column, and (c) establishing the efficiency of separation by an adsorptive process due to repeated averaging of the base kinetic property. That is why the LDF model works in practice.
    Type of Medium: Electronic Resource
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  • 14
    ISSN: 1572-879X
    Keywords: ammonia synthesis ; kinetics ; ruthenium catalysts ; promotional effect
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of NH3 synthesis over carbon-based ruthenium catalysts promoted with barium or alkali was studied. Both the ammonia partial pressure dependencies of the reaction rates (T = 400°C, p = 63 bar, H2 : N2 = 3 : 1) and the pressure variations of the activity (T = 370°C, p= 4–63 bar, H2 : NN2 = 3 : 1) were found to be different for Ba and for the alkali (K, Cs). Ba–Ru/C proved to be more sensitive to the NH3 content and to the total pressure. The rate of synthesis over the alkali-promoted catalysts is, in turn, much stronger influenced by the ruthenium dispersion. TOFs of NH3 synthesis for the promoted samples at 370°C and 4 bar (Ba 0.085 1/s, Cs 0.05 1/s, K 0.035 1/s) are significantly higher than that for the Ru(0001) basal plane (0.0085 1/s results from the literature data at 370°C, 2 bar). The most active Ru/C samples (Ba or Cs) exceed significantly the fused iron catalyst, especially at high conversions.
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  • 15
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    Topics in catalysis 11-12 (2000), S. 327-333 
    ISSN: 1572-9028
    Keywords: hydrodenitrogenation ; toluidine ; methylcyclohexylamine ; kinetics ; nickel-promoted molybdenum sulphide
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The hydrodenitrogenation (HDN) of o-toluidine and its reaction intermediates was studied over a NiMo/γ-Al2O3 catalyst. The kinetics of the HDN of methylcyclohexylamine and of the hydrogenation of cyclohexene were also studied. Hydrogenation of o-toluidine alone produces methylcyclohexene and methylcyclohexane. When a sufficient quantity of cyclohexene is added during the HDN of toluidine, methylcyclohexylamine, the first intermediate in the hydrogenation of toluidine, becomes detectable. Because of its strong adsorption constant and high rate constant for reacting further to methylcyclohexene and methylcyclohexane, methylcyclohexylamine is not observed in the HDN of toluidine. Adding cyclohexene decreases the adsorption of methylcyclohexylamine, thus enabling its detection. The rate and adsorption constants of methylcyclohexylamine and cyclohexene in the HDN of methylcyclohexylamine were calculated by fitting the kinetic data to a Langmuir–Hinshelwood equation. A two-site model was used to describe the surface reactions, with one site for the methylcyclohexylamine reactions and the other for the cyclohexene reaction.
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  • 16
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    Adsorption 6 (2000), S. 349-357 
    ISSN: 1572-8757
    Keywords: sulfadiazene ; adsorption ; kinetics
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    Topics: Chemistry and Pharmacology , Physics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract To investigate the nature of interactive forces between sulfadiazene molecules and alumina surface the experiments were performed for the adsorption of sulfadiazene (SD) from its aqueous sulution onto the alumina surfaces at 25 ± 0.2°C and the influence of factors such as increasing concentration of SD (4.0–20.0 × 10−3 mol cm−3), the time required for adsorption equilibrium, pH (2.0–12.0) and temperature (5–45°C) of the adsorption medium, the presence of ions like Cl−, SO2− 4 and PO3− 4 (0.01–0.30 M) and organic solvents (5% v/v) were observed on the course of adsorption of SD. Various adsorption and kinetic parameters such as adsorption coefficient, the rate constants for adsorption and desorption were also evaluated. The results of the above cited studies facilitated to formulate the mechanisms of interaction between SD and alumina surfaces. From application view point the present work may be a potential tool for an effective chromatographic separation of sulfa drugs from industrial effluents.
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  • 17
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    Catalysis letters 64 (2000), S. 65-75 
    ISSN: 1572-879X
    Keywords: NO reduction ; CH3OH ; La2O3 ; methyl nitrite ; kinetics
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Nitric oxide (NO) reduction by methanol was studied over La2O3 in the presence and absence of oxygen. In the absence of O2, CH3OH reduced NO to both N2O and N2, with selectivity to dinitrogen formation decreasing from around 85% at 623 K to 50–70% at 723 K. With 1% O2 in the feed, rates were 4–8 times higher, but the selectivity to N2 dropped from 50% at 623 K to 10% at 723 K. The specific activities with La2O3 for this reaction were higher than those for other reductants; for example, at 773 K with hydrogen a specific activity of 35 μmol NO/s m2 was obtained whereas that for methanol was 600 μmol NO/s m2. The Arrhenius plots were linear under differential reaction conditions, and the apparent activation energy was consistently near 14 kcal/mol with CH3OH. Linear partial pressure dependencies based on a power rate law were obtained and showed a near‐zero order in CH3OH and a near‐first order in H2. In the absence of O2, a Langmuir–Hinshelwood type model assuming a surface reaction between adsorbed CH3OH and adsorbed NO as the slow step satisfactorily fitted the data, and the model invoking two types of sites provided the best fit and gave thermodynamically consistent rate constants. In the presence of O2 a homogeneous gas‐phase reaction between O2, NO, and CH3OH occurred to yield methyl nitrite. This reaction converted more than 30% of the methanol at 300 K and continued to occur up to temperatures where methanol was fully oxidized. Quantitative kinetic studies of the heterogeneous reaction with O2 present were significantly complicated by this homogeneous reaction.
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  • 18
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    Catalysis letters 69 (2000), S. 103-107 
    ISSN: 1572-879X
    Keywords: dicyclopentadiene ; Wacker oxidation ; Pd(AcO)2 ; benzoquinone ; kinetics
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The oxidation of dicyclopentadiene catalyzed by palladium(II) acetate and benzoquinone in the presence of perchloric acid was studied. Tricyclodecenone in high selectivity (85–98%) at a conversion of dicyclopentadiene up to 76% was obtained. The kinetic model assumed the significant inhibition complexation between dicyclopentadiene and tricyclodecenone with the catalytic species.
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  • 19
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    Journal of thermal analysis and calorimetry 59 (2000), S. 633-642 
    ISSN: 1572-8943
    Keywords: cadmium ; dialkyldithiocarbamate ; kinetics ; thermal decomposition ; thermogravimetry
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The thermal decomposition kinetics of the solid complexes Cd(S2 CNR2 )2 , where R =C2 H5 , n -C3 H7 , n -C4 H9 or iso -C4 H9 , was studied by using isothermal and non-isothermal thermogravimetry. The superimposed TG/DTG/DSC curves revealed that thermal decomposition reactions occur in the liquid phase. The kinetic model that best fitted the experimental isothermal TG data was the one-dimensional phase-boundary reaction-controlled process R1 . The thermal analysis data suggested the thermal stability sequence Cd(S2 CNBun 2 )2 〉Cd(S2 CNPrn 2 )2 〉Cd(S2 CNBui 2 )2 〉Cd(S2 CNEt2 )2 , which accords with the sequence of stability of the apparent activation energies.
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  • 20
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    Journal of thermal analysis and calorimetry 59 (2000), S. 807-814 
    ISSN: 1572-8943
    Keywords: facial and meridional Co(III) complexes ; kinetics ; thermodynamics
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Thermal properties of facial and meridional uns-cis-[Co(eddp)gly]0.5H2O complexes were investigated by means of DSC and TG techniques. It wasshown that the processes of thermal decomposition of these complexes are multi-stepdegradation processes, which can also be well separated into individual steps, depending onthe molecular symmetry. Thus, the process of thermal degradation of the meridional isomerof the above complex consists of 4 well-separated steps in the temperature interval from 100to 500°C. The corresponding kinetic and thermodynamic parameters of this process weredetermined, and a possible mechanism is discussed.
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    Journal of thermal analysis and calorimetry 61 (2000), S. 955-965 
    ISSN: 1572-8943
    Keywords: kinetics ; metal complexes
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Thermogravimetry (TG) and differential thermal analysis (DTA) were performed on the complexes with general formula (M(DEBT)n (where M =Fe, Co, Ni, Cu or Ru; n =2, or 3 and DEBT=N,N-diethyl-N'-benzoylthiourea). Derivative thermogravimetric (DTG) curves were also recorded in order to obtain decomposition data on the complexes. The complexes of Fe(III), Co(II), Ni(II), Cu(II) and Ru(III) displayed two- or three-stage decomposition patterns when heated in a dynamic nitrogen atmosphere. Mass loss considerations relating to the decomposition stages indicated the conversion of the complexes to the sulfides or to the corresponding metal alone (Cu, Ru, NiS, CoS or FeS). Mathematical analysis of the TG and DTG data showed that the order of reaction varied between 0.395 and 0.973. Kinetic parameters such as the decomposition energy, the entropy of activation and the pre-exponential factor are reported.
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  • 22
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    Journal of thermal analysis and calorimetry 62 (2000), S. 429-433 
    ISSN: 1572-8943
    Keywords: adsorption ; fast measurement ; gravimetry ; kinetics ; sorption ; kw6
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Jäntti introduced a method to reduce the time required for the stepwise measurement of adsorption isotherms. After each pressure change he measured the adsorbed mass three times and calculated its equilibrium value at the new pressure. In the present paper, we discuss the applicability of this method in a broader scope without starting from a given combination of sorptive and adsorbent and the influence of measuring inaccuracies. The method is applied to detect whether the adsorption process is based on more than one adsorption mechanism or not.
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  • 23
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    Journal of thermal analysis and calorimetry 63 (2000), S. 375-386 
    ISSN: 1572-8943
    Keywords: activation energy ; ammonium perchlorate ; decompositon ; isothermal ; kinetics ; thermogravimetry
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of the thermal decomposition of ammonium perchlorate at temperatures between 215 and 260°C is studied, in this work, by measuring the sample mass loss as a function of time applying the isothermal thermogravimetric method. From the maximum decomposition rate – temperature dependence two different decomposition stages, corresponding to two different structural phases of ammonium perchlorate, are identified. For the first region (215–235°C), corresponding to the orthorhombic phase, the mean value of the activation energy of 146.3 kJ mol–1, and the pre-exponential factor of 3.43⋅1014 min–1 are obtained, whereas for the second region (240–260°C), corresponding to the cubic phase, the mean value of the activation energy of153.3 kJ mol–1, and the pre-exponential factor of 4.11⋅1014 min–1 are obtained.
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  • 24
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    Journal of thermal analysis and calorimetry 60 (2000), S. 35-43 
    ISSN: 1572-8943
    Keywords: kinetics ; 10-methylacridinium halides ; thermodynamics ; thermogravimetric investigations
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    Topics: Chemistry and Pharmacology
    Notes: Abstract 10-Methylacridinium chloride, bromide and iodide were prepared in crystalline forms (the first two salts as monohydrates) and subjected to thermogravimetric investigations. Decomposition of the compounds is initially accompanied by the liberation of water (in case of monohydrates), halomethanes and acridine molecules. As decomposition proceeds, side reactions occur which are reflected in a complex pattern of thermogravimetric curves. TG traces corresponding to the initial decomposition stage were used to determine the kinetic characteristics of the thermal dissociation of the salts. MNDO/d, AM1 and PM3 methods were employed independently to examine reaction pathways and to predict thermodynamic and kinetic barriers for the thermal decomposition of the compounds. These data were subsequently supplemented with theoretically determined crystal lattice energies, which enabled the relevant characteristics for the decomposition of crystalline phases to be predicted. The theoretically predicted characteristics are qualitatively comparable with those originating from thermogravimetric investigations, which allows one to believe that both are valid.
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  • 25
    ISSN: 1572-8943
    Keywords: cyanazine ; DSC ; kinetics ; thermal stability
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Cyanazine was taken as an example for investigations under the influence of different conditions on thermal decomposition of triazine herbicides. DSC measurements were carried out under atmospheric pressure and hermetically closed, under pressure 1.3 kPa. The influence of the pressure on the constant reaction rate of decomposition of cyanazine was discussed. It was also proved that the predicted reaction constant rates from isothermal and non-isothermal measurements are consistent.
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  • 26
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    Journal of thermal analysis and calorimetry 60 (2000), S. 247-255 
    ISSN: 1572-8943
    Keywords: desulfuration ; gas atmosphere ; kinetics ; thermal decomposition ; titanium dioxide
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The studies were devoted to determination of the effect of gas atmosphere and its pressure on the second step of decomposition of hydrated titanium dioxide (HTD) promoted by sulfate groups. It has been found that thermal decomposition of HTD at temperatures above 300°C consists of a number of processes such as dehydroxylation, desulfuration, recrystallization and sintering of solid grains, photochemical processes (if the decomposition proceeds in the presence of light) and adsorption of gas phase components (in the presence of air or SO2). Kinetic parameters characterizing this step of decomposition have been determined for processes carried out in vacuum and in argon or air atmospheres (at a pressure of 13.33hPa). The kinetic curves of decomposition carried out in the presence of gases capable of being adsorbed on the surface of partly dehydrated HTD are featured by local extrema due to simultaneous processes of decomposition and adsorption of gas components.
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    Journal of thermal analysis and calorimetry 60 (2000), S. 9-15 
    ISSN: 1572-8943
    Keywords: coordination compounds ; kinetics ; thermal dissociation
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Physicalo-chemical importance of the quantitative study of kineticliability of coordination compounds in thermal dissociation processes is considered. Muchattention is given to the proof of the physicalo-chemical meaning and validity of kineticparameters calculated from thermoanalytical data. Experimental data (thermal dissociation ofcoordination compounds and clathrates with such a matrix) are discussed.
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    Journal of thermal analysis and calorimetry 60 (2000), S. 401-407 
    ISSN: 1572-8943
    Keywords: cross-linking ; isothermal crystallization ; kinetics ; modification ; polypropylene ; silica
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The effect of addition of silica on the parameters of isothermal crystallization of polypropylene has been investigated. It was found that the covering of the silica surface by a layer of low-density polyethylene leads to a deactivation of the filler regarding the positive effect on the polypropylene crystallization rate parameters. Cross-linking of the surface polyethylene layer results in a stronger attachment of the modifying polymer to the filler surface and the deactivation effect of the silica surface modification is more pronounced.
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  • 29
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    Journal of thermal analysis and calorimetry 60 (2000), S. 541-547 
    ISSN: 1572-8943
    Keywords: Cr(II) ; chromium trioxide ; kinetics ; reduction ; thermal analysis
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The thermal behaviour of CrO3 on heating up to 600°C in dynamic atmospheres of air, N2 and H2 was examined by thermogravimetry (TG), differential thermal analysis (DTA), IR spectroscopy and diffuse reflectance spectroscopy (DRS). The results revealed three major thermal events, depending to different extents on the surrounding atmosphere: (i) melting of CrO3 near 215°C (independent of the atmosphere), (ii) decomposition into Cr2(CrO4)3 at 340–360°C (insignificantly dependent), and (iii) decomposition of the chromate into Cr2O3 at 415–490°C (significantly dependent). The decomposition CrO3 → Cr2(CrO4)3 is largely thermal and involves exothermic deoxygenation and polymerization reactions, whereas the decomposition Cr2(CrO4)3 → Cr2O3 involves endothermic reductive deoxygenation reactions in air (or N2) which are greatly accelerated and rendered exothermic in the presence of H2. TG measurements as a function of heating rate (2–50°C min−1) demonstrated the acceleratory role of H2, which extended to the formation of Cr(II) species. This could sustain a mechanism whereby H2 molecules are considered to chemisorb dissociatively, and then spillover to induce the reduction. DTA measurements as a function of the heating rate (2–50°C min−1) helped in the derivation of non-isothermal kinetic parameters strongly supportive of the mechanism envisaged.
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    Journal of thermal analysis and calorimetry 60 (2000), S. 667-674 
    ISSN: 1572-8943
    Keywords: accommodation function ; crystal growth ; glass-ceramics ; kinetics ; number of nuclei ; thermal history
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Kinetic modeling of the crystal growth from pre-existing nuclei was reexamined to obtain a fundamental information about the controlled crystallization of glasses during formation of advanced inorganic glass-ceramics. Methods of kinetic analysis were reviewed by taking account of thermal history of the sample within the temperature range of nucleation. An accommodation function depending on the thermal history was introduced in the kinetic equation. The role of the accommodation function was reinvestigated when determining the activation energy from a series of kinetic curves. The kinetic description of the crystal growth in the samples with different thermal history was generalized by extrapolating the rate behavior to infinite temperature.
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    Journal of thermal analysis and calorimetry 60 (2000), S. 333-343 
    ISSN: 1572-8943
    Keywords: base line ; DSC ; kinetics ; modeling ; thermodynamics ; TMDSC
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The application of non-linear heating program to a heat-flux DSC apparatus has attracted much attention. From thermodynamics viewpoint, it is shown that the variation of enthalpy of a sample changing with temperature change is due, to both the true heat capacity of the sample and the enthalpy of some transformations occurring in the sample, characterized by its degree of advance. Using the simple assumption that the rate of the transformation is proportional to the distance from the thermodynamic equilibrium, an electrical model of the thermal event is given. Using the coupled cell model of the DSC apparatus, we show how to obtain the rate of transformation of the sample and heat capacity, which is directly related to the base line of the experiment.
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    Journal of thermal analysis and calorimetry 60 (2000), S. 759-778 
    ISSN: 1572-8943
    Keywords: decomposition temperature ; error sources ; gas-flow and vapor control ; kinetics ; thermogravimetry
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The well-known divergence between the present ‘state of the art’ of thermogravimetry and industrial requirements is discussed. Sources of errors are analyzed and the optimization of measuring conditions is discussed regarding the problems associated with static and dynamic (flow) atmospheres, and interactions between materials and gases or vapors. Recommendations for gas-flow control systems and vapor sources are given. Thermal stability and the kinetics of gas-evolving, reversible, thermal decompositions of solids are discussed. The scope of TG-derived kinetics for practical use is examined. Some new characteristic points of TG curves are proposed and defined, e.g. ‘procedure-independent decomposition temperature’ and ‘augmented decomposition temperature’ (obtained at pseudo-equilibrium conditions).
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    Journal of thermal analysis and calorimetry 60 (2000), S. 879-886 
    ISSN: 1572-8943
    Keywords: driving force ; kinetics ; rate equation ; reversible reactions
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    Topics: Chemistry and Pharmacology
    Notes: Abstract This paper outlines the different ways of taking the distance from thermodynamic equilibrium into account in kinetic studies based on thermoanalytical experiments. The three main approaches are: (i) avoiding or neglecting the effect of the reverse reaction, (ii) describing the influence of distance from equilibrium on apparent kinetic parameters, and (iii) incorporating a driving force factor in the rate equation. Finally, the contradiction of the microscopic nature of the processes and the macroscopic character of the usual rate equation are briefly discussed.
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    Journal of thermal analysis and calorimetry 60 (2000), S. 943-954 
    ISSN: 1572-8943
    Keywords: CRTA ; kinetics ; self-generated atmospheric conditions ; synthetic malachite ; thermal decomposition
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetic behavior of the thermal decomposition of synthetic malachite was investigated by means of CRTA under different conditions of reduced pressure, flowing gases and quasi-isobaric atmospheres. The thermal decomposition was found to proceed at lower temperatures under the influence of the self-generated gases, CO2 and H2O. From a viewpoint of chemical equilibrium, the normal and opposite effects on the overall kinetics were observed for the self-generated CO2 and H2O, respectively. The complexity of the present reaction is also reflected by the variations of the apparent kinetic parameters which depend on the applied and self-generated atmospheric conditions. The practical usefulness of CRTA when applied to a complicated thermal decomposition is discussed as exemplified by the kinetic approaches to the present reaction.
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    Journal of thermal analysis and calorimetry 61 (2000), S. 151-156 
    ISSN: 1572-8943
    Keywords: complexes ; kinetics ; TG-DTA
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Thermal behaviour of a few lanthanide complexes of the type ML3(I) [M=Eu,Gd; HL=4,4,4-trifluoro- 1-(2-napthyl)-1,3-butanedione and EuL30.5dmm dmm=2,6-dimethylmorpholine(II)], has been investigated. From thermogravimetric(TG) curves, the decomposition pattern of the compounds has been analysed on the basis of mass loss data. The order and activation energy of the thermal decomposition reactions have been elucidated. From differential thermal analysis (DTA) studies, the heat of reaction and rate of thermal decomposition reaction have been enumerated.
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    Journal of thermal analysis and calorimetry 61 (2000), S. 239-242 
    ISSN: 1572-8943
    Keywords: kinetics ; Mannich compounds ; thermal decomposition
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The authors present data concerning the evaluation of kinetic parameters of the decomposition of a Mannich compound by using the classical method of constant heating rate thermal analysis and the new one of controlled rate thermal analysis (CRTA). The data processed using the CRTA method allow to obtain more reliable kinetic parameters according to the proposed reaction mechanism.
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    Journal of thermal analysis and calorimetry 61 (2000), S. 437-450 
    ISSN: 1572-8943
    Keywords: crystallization ; EPDM ; kinetics ; morphology ; PP ; rubber
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The effect of the incorporation of an amorphous immiscible polymer (ethylene-propylene-diene- terpolymer) on the PP crystallization kinetics and thermodynamics is investigated by thermal analysis. The results of the investigation have shown that EPDM acts as a nucleant agent. A marked decrease of the half time of PP crystallization, τ1/2 , as well as a sensible increase of the overall crystallization rate, K n , has been observed in the presence of EPDM. Moreover, at any crystallization temperature, a minimum of τ1/2 , is obtained at 25% EPDM content in the blend. The Avrami model has been successfully applied to describe the crystallization kinetics of the blend. The kinetic curves obtained under non-isothermal conditions confirm the results obtained under isothermal conditions and demonstrate the nucleant action of the EPDM phase on the PP crystallization.
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    Journal of thermal analysis and calorimetry 62 (2000), S. 721-727 
    ISSN: 1572-8943
    Keywords: kinetics ; metal exchange ; thermaldehydration ; zeolite
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Zeolite-4A is a hydrated aluminosilicate which becomes more hydrated when exchanged with transition metals. In this work, the dehydration kinetics of cobalt, nickel and copper(II)-exchanged zeolite-4A were studied by means of TG and DTA over the temperature range from 20 to 500°C, and the numbers of water molecules in the metal-exchanged zeolite samples were calculated. It was observed that, as the ionic radius of the hydrated metal increased, the number of water molecules also increased. The loss of water from the zeolite samples generally occurred in the temperature range 100–300°C and was manifested in the DTA graphs by an extended endothermic effect. The DTA curves demonstrated that the peak position shifted towards lower temperatures as the metal concentration increased or, in other words, the water of hydration increased. The kinetic parameters (order of reaction and activation energy) were calculated via the Coats and Redfern method. The process of dehydration was found to follow first-order kinetics.
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    Journal of thermal analysis and calorimetry 63 (2000), S. 359-374 
    ISSN: 1572-8943
    Keywords: KEKAM equation ; kinetics ; thermal dissociation of solids
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Relationships have been established between the average conversion degree and the dissociation time for polydisperse granular material, taking its grain size distribution into account. It has been checked in which cases the kinetic curves obtained by a numerical solution can be described in terms of KEKAM equation.
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  • 40
    ISSN: 1572-8943
    Keywords: isoconversional methods ; kinetics
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    Notes: Abstract An analysis is presented of the consequences of the use of a one term equation containing apparent activation parameters, instead of the true rate equation to describe two successive decomposition reactions undergone by a solid compound. It is demonstrated that the apparent activation energy, obtained by means of isoconversional differential and integral methods, varies with the conversion degree for a relatively narrow temperature range and with temperature at a given value of the conversion degree. The activation energy values obtained with the isoconversional differential method are higher than the corresponding values obtained with the isoconversional integral method.
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    Journal of thermal analysis and calorimetry 59 (2000), S. 869-875 
    ISSN: 1572-8943
    Keywords: decomposition ; kinetics ; plumbo-jarosite
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    Topics: Chemistry and Pharmacology
    Notes: Abstract An investigation was carried out on the kinetics of thermal decomposition of plumbo-jarosite. The kinetic models of dissociation of the compounds in the ore were identified. The results of the kinetic studies and the mechanism of the process are discussed. The thermal decomposition of plumbo-jarosite occurs in three stages: the first up to 763, the second up to 1023 and the third up to 1223 K, the corresponding activation energy values being 62.2, 60.3 and 98.0 kJ mol–1 , respectively.
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    Journal of thermal analysis and calorimetry 61 (2000), S. 805-818 
    ISSN: 1572-8943
    Keywords: aluminium ; ARC ; DSC ; kinetics ; nanometric size ; SDT ; TG
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The thermal properties of Alex, a nanosized Al powder, were determined using various techniques, including DSC, TG, simultaneous TG-DTA (SDT) and accelerating rate calorimetry (ARC). The results demonstrate that the specific heat capacities of nano and micron size Al powders are similar between 30 and 400°C. Dynamic and isothermal methods were used to determine the kinetic parameters for the oxidation reaction of Alex, which was detected at an onset temperature of 481°C. The results obtained were in good agreement with each other. From the ARC experiments, exotherms were detected near 340 and 260°C for experiments started at ambient pressure and at 0.72 MPa, respectively.
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  • 43
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    Journal of thermal analysis and calorimetry 61 (2000), S. 861-871 
    ISSN: 1572-8943
    Keywords: DAGN ; kinetics ; mechanism and IR spectroscopy ; TAGN ; thermal decomposition
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Diaminoguanidine nitrate (DAGN) and triaminoguanidine nitrate (TAGN),potential energetic materials in emerging propulsion technology with high mass impetus at low isochoric flame temperature have been studied as regards kinetics and mechanism of thermal decomposition using thermogravimetry (TG), differential thermal analysis (DTA),infrared spectroscopy (IR) and hot stage microscopy. Kinetics of thermolysis has been followed by isothermal TG and IR. For the initial stage of thermolysis of DAGN the best linearity with a correlation coefficient of 0.9976 was obtained for the Avrami-Erofe'evequation, n=2, by isothermal TG. The activation energy was found to be 130 kJ mol–1 and logA=11.4. The initial stage of thermolysis of TAGN also obeyed the Avrami-Erofe'ev equation, n=2, with a correlation coefficient of 0.9975by isothermal TG and the kinetic parameters are E=160.0 kJ mol–1 and logA=16.0. High temperature IR spectra showed exquisite preferential loss in intensity of the NH2, NH, N–N stretching and CNN bending. Spectroscopic and other results favour deamination reaction involving the rupture of the N–N bond as the primary step in the thermal decomposition.
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  • 44
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    Journal of thermal analysis and calorimetry 61 (2000), S. 979-984 
    ISSN: 1572-8943
    Keywords: kinetics ; nucleation-growth
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The author presents some applications of the fractal geometry in the kinetics of heterogeneous decomposition of solids.
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  • 45
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    Journal of thermal analysis and calorimetry 59 (2000), S. 935-942 
    ISSN: 1572-8943
    Keywords: CoSO46H2O ; kinetics ; thermal decomposition
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Thermogravimetry (TG-DTG), and differential thermal analysis (DTA) were used in the study of the kinetics of decomposition of cobalt sulphate hexahydrate under an air atmosphere. The kinetics of the particular stages of CoSO4 6H2 O decomposition were evaluated from the dynamic mass loss data. The values of the kinetic parameters for each stage of the thermal decomposition were calculated from the α(T) data by using the integral method, applying the Coats-Redfern approximation.
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  • 46
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    Journal of thermal analysis and calorimetry 62 (2000), S. 681-685 
    ISSN: 1572-8943
    Keywords: coal-burning additive ; combustion ; graphite ; kinetics
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The catalytic and accelerating effects of three coal-burning additives (CBA) on the burning of graphite were studied with the help of thermogravimetric (TG) analysis. The kinetic study on the catalytic oxidation of the graphite doped with CBA was carried out and the results were presented. The results show that the CBA can change the carbon oxidation/combustion course by catalytic action and change the activation energy, thus improving the combustion efficiency.
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  • 47
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    Journal of thermal analysis and calorimetry 63 (2000), S. 457-463 
    ISSN: 1572-8943
    Keywords: isoconversional methods ; kinetics
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    Topics: Chemistry and Pharmacology
    Notes: Abstract It is demonstrated that, if the activation energy depends on the degree of conversion, its values obtained by isoconversional differential and integral methods are different.
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  • 48
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    Journal of materials synthesis and processing 8 (2000), S. 139-144 
    ISSN: 1573-4870
    Keywords: TiO2 ; phase transformations ; mechanical alloying ; kinetics ; modeling
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    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract A high-pressure and high-temperature phase of TiO2 : TiO2 II is formed transiently during room-temperature high-energy ball milling of anatase TiO2 : TiO2 anatase → TiO2 II → TiO2 rutile. Rutile is the only phase present after prolonged ball milling. The present paper focuses on the influences of physical and chemical processing conditions on the transformation kinetics. The effects of two milling parameters on the kinetics of phase transformation of anatase TiO2 were investigated: the nature of milling tools and the powder-to-ball weight ratio R. Granulometric characterizations and TEM observations have demonstrated that the transformation of TiO2 anatase into TiO2 II occurs without fracturing of particles and that TiO2 II nanograins form at the surface of anatase particles. The parameter R affects only the transformation rate. For a given R, the transformation rate is the largest with alumina grinding tools, intermediate with zirconia tools, and the smallest with steel tools. The parameters involved in current models of the mechanical alloying process do not suffice to explain the differences in transformation rates observed here. A parameter, which takes into account the influence of the mechanical properties of grinding materials, is considered.
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  • 49
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    Journal of materials synthesis and processing 8 (2000), S. 271-277 
    ISSN: 1573-4870
    Keywords: Comminution ; kinetics ; mechanical alloying ; phase transformation
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    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract It has been shown that structural evolution occurring in powder mixtures subjected to mechanical treatment by milling follow well-defined conversion trends as a function of milling time. Sigmoidal curves were observed in the case of the mechanical alloying of transition metal mixtures, whereas a simpler kinetic course with a progressively decreasing transformation rate was found to characterize the disordering process of intermetallic equilibrium compounds by mechanical milling. Under the stipulation that collisions are the dominant energy transfer events, a kinetic model is developed to relate the observed macrokinetic features to the discrete powder fractions, which transform at each impact. Because of its intrinsic qualities, the milling process was regarded as discrete processing. A statistical approach was followed to work out a set of differential equations, solutions of which provide a sound description of the transformation kinetics in terms of conventional rate expressions. The model allows one to reproduce the different kinetic behaviors by means of a single, unifying mathematical formalism. Furthermore, quantifying the structural evolution rate by suitable kinetic constants permits the exploration of the reactive behavior of a system treated under different milling regimes or to compare, on an absolute basis, different systems processed under similar conditions.
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  • 50
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    Oxidation of metals 53 (2000), S. 351-360 
    ISSN: 1573-4889
    Keywords: Co-base superalloy ; high-temperature oxidation ; kinetics ; structure
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    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The oxidation behavior of the Co-base superalloy DZ40M was studied in air at900–1100°C for times of up to 2000 hr. The results indicated thatthis alloy can grow a protective oxide scale at 900 and 1000°C duringisothermal oxidation, but not at 1100°C because of serious cracking andspalling of the oxide scales. Moreover, an internal-precipitate zone formedin the subsurface region of the alloy at all temperatures and times. Theprecipitates were rich in Cr in the vicinity of the alloy–scaleinterface and rich in Al deep in the alloy. The internal-precipitatemorphology changed from a granular to needlelike shape with increasingoxidation temperature.
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  • 51
    ISSN: 1573-4943
    Keywords: Aluminum ; yeast hexokinase ; preferential interactions ; kinetics
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The aluminum and yeast hexokinase interaction was studied. Structural changes were correlated with variations in protein functionality. Results show two different behaviors: At low metal concentrations preferential adsorption of metal (and water exclusion) induces aggregate formation. No significant changes in the protein structure occur, but there is a continuous loss of activity (from the first concentration). At large salt concentrations a monomerization process and a conformational change in the secondary structure as well as in the three-dimensional structure take place. This change reduces the percentage of α-helix conformation, gives thermal stability to the protein, and allows the exposure of some tryptophan residue and hydrophobic regions. The protein inhibition increases. Conformational change and monomerization may allow access of the metal to the substrate site, mainly the ATP site. The inhibition in any case is of mixed type with a competitive component.
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  • 52
    ISSN: 1573-4943
    Keywords: Creatine kinase ; human ; expression ; brain ; muscle ; purification ; kinetics
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    Topics: Chemistry and Pharmacology
    Notes: Abstract We report the expression of the human muscle (CK-MM) and brain (CK-BB) creatine kinases in Escherichia coli. The proteins have been purified to apparent homogeneity and several of their physical and kinetic properties investigated. In the process, we have conclusively verified the correct DNA sequence of the genes encoding the respective isozymes, and determined the correct primary structure and mass of the gene products. Alignment of the primary sequences of these two enzymes shows 81% sequence identity with each other, and no obvious gross structural differences. However, Western blot analyses demonstrated the general lack of antigenic cross-reactivity between these isozymes. Preliminary kinetic analyses show the K m and k cat values for the creatine and MgATP substrates are similar to values reported for other isozymes from various tissues and organisms. The human muscle and brain CKs do not, however, exhibit the synergism of substrate binding that is observed, for example, in rabbit muscle creatine kinase.
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  • 53
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    Russian chemical bulletin 49 (2000), S. 1974-1976 
    ISSN: 1573-9171
    Keywords: ammonium dinitramide ; thermal decomposition ; kinetics ; stabilization ; isotope composition
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of accumulation of the main products of thermal decomposition of ammonium dinitramide in the melt was investigated. The isotope composition of nitrogen-containing gases evolved by the decomposition of 15NH4N(NO2)2 and NH4 15N(NO2)2 was found. Easily oxidized salts, amines, amides, iodides, and other compounds soluble in the melt interfere with the liquid-phase decomposition of ammonium dinitramide.
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  • 54
    ISSN: 1573-9171
    Keywords: 2-alkylthiopropenals ; Diels–Alder reaction ; kinetics ; reaction mechanism ; 2,5-dialkylthio-3,4-dihydro-2H-pyran-2-carbaldehyde ; IR spectroscopy ; ab initio calculations
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of 2-alkylthiopropenals cyclodimerization was studied in the temperature range from -7 to +42 °C in heptane and at 20 °C in various solvents. The rate constants for cyclodimerization of 2-alkylthiopropenals are four orders of magnitude higher than those for dimerization of the oxygen-containing analogs, 2-alkoxypropenals, and are independent of the solvent polarity and substituent steric constant. The activation parameters for 2-butylthiopropenal cyclodimerization were estimated. The distribution of electron density in the 2-methoxy- and 2-methylthiopropenals molecules was calculated by the ab initio method. From comparison of the HOMO and LUMO energies for these aldehydes it was concluded that the ratio between the cyclodimerization rates for 2-alkylthio-, 2-ethoxypropenals, and propenal is determined by the HOMO–LUMO gap.
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  • 55
    ISSN: 1608-3245
    Keywords: DNA ; kinetics ; oligonucleotide derivatives ; photomodification ; sensitization
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    Topics: Biology
    Notes: Abstract Quantitative characteristics of thermodynamic and kinetic cooperativity arising in the process of photomodification of a single-stranded DNA fragment with binary systems of oligonucleotide conjugates forming an active site on the target were studied. Oligonucleotides of the binary system were complementary to adjacent segments of the DNA target, and contained arylazide (X) and perylene (S) residues covalently attached to their terminal phosphates. Upon irradiation at the perylene absorption wavelength, the target was modified by the arylazide residue, which was activated owing to the contiguity with the sensitizing perylene group in the tandem complex. Basing on the kinetic data, the constants of association of both derivatives of oligonucleotides with the target were determined: K x = 1.13 · 106 M–1, K s = 1.49 · 104 M–1. It was determined that association of both oligonucleotides with the target proceeded with a positive cooperativity characterized by parameter α = 45. The kinetic cooperativity parameter β was found to be approximately equal to 200; this characterized the acceleration of target modification in complex with the binary reagent versus that in the absence of sensitizer.
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  • 56
    ISSN: 1608-3407
    Keywords: Dunaliella salina ; lactate dehydrogenase ; kinetics ; glycerol synthesis
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    Topics: Biology
    Notes: Abstract The dependence of the catalytic properties of lactate dehydrogenase (LDH, EC 1.1.1.27) from a halophilic alga Dunaliella salina, a glycophilic alga Chlamydomonas reinhardtii, and from porcine muscle on glycerol concentration, medium pH, and temperature was investigated. Several chemical properties of the enzyme from D. salina differentiated it from the LDH preparation obtained from C. reinhardtii and any homologous enzymes of plant, animal, and bacterial origin. (1) V max of pyruvate reduction manifested low sensitivity to the major intracellular osmolyte, glycerol. (2) The affinity of LDH for its coenzyme NADH dropped in the physiological pH region of 6–8. Above pH 8, NADH virtually did not bind to LDH, while the enzyme affinity for pyruvate did not change considerably. (3) The enzyme thermostability was extremely low: LDH was completely inactivated at room temperature within 30 min. The optimum temperature for pyruvate reduction (32°C) was considerably lower than with the enzyme preparations from C. reinhardtii (52°C) and porcine muscle (61°C). (4) NADH greatly stabilized LDH: the ratio of LDH inactivation constants in the absence of the coenzyme and after NADH addition at the optimum temperature in the preparation from D. salina exceeded the corresponding indices of LDH preparations from C. reinhardtii twelve times and from porcine muscle eight times. The authors believe that these LDH properties match the specific metabolism of D. salina which is set at rapid glycerol synthesis under hyperosmotic stress conditions. The increase of cytoplasmic pH value produced in D. salina by the hyperosmotic shock can switch off the terminal reaction of the glycolytic pathway and thus provide for the most efficient utilization of NADH in the cycle of glycerol synthesis. As LDH is destabilized in the absence of NADH, this reaction is also switched off. In the course of alga adaptation to the hyperosmotic shock, glycerol accumulation and the neutralization of intracellular pH stabilize LDH, thus creating the conditions for restoring the complete glycolytic cycle.
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  • 57
    ISSN: 1573-4986
    Keywords: β-glycosidase ; temperature dependence ; kinetics ; glucose ; transglycosylation ; (Thermus thermophilus)
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    Topics: Chemistry and Pharmacology
    Notes: Abstract A β-glycosidase of a thermophile, Thermus thermophilus, belonging to the glycoside hydrolase family 1, was cloned and overexpressed in Escherichia coli. The purified enzyme (Ttβgly) has a broad substrate specificity towards β-D-glucoside, β-D-galactoside and β-D-fucoside derivatives. The thermostability of Ttβgly was exploited to study its kinetic properties within the range 25–80[emsp4 ]°C. Whatever the temperature, except around 60[emsp4 ]°C, the enzyme displayed non-Michaelian kinetic behavior. Ttβgly was inhibited by high concentrations of substrate below 60[emsp4 ]°C and was activated by high concentrations of substrate above 60[emsp4 ]°C. The apparent kinetic parameters (k cat and K m ) were calculated at different temperatures. Both k cat and K m increased with an increase in temperature, but up to 75[emsp4 ]°C the values of k cat increased much more rapidly than the values of K m . The observed kinetics might be due to a combination of factors including inhibition by excess substrate and stimulation due to transglycosylation reactions. Our results show that the substrate could act not only as a glycosyl donor but also as a glycosyl acceptor. In addition, when the glucose was added to reaction mixtures, inhibition or activation was observed depending on both substrate concentration and temperature. A reaction model is proposed to explain the kinetic behavior of Ttβgly. The scheme integrates the inhibition observed at high concentrations of substrate and the activation due to transglycosylation reactions implicating the existence of a transfer subsite.
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  • 58
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    Journal of applied spectroscopy 67 (2000), S. 981-989 
    ISSN: 1573-8647
    Keywords: nonlinear regime of stimulated Raman scattering ; fluctuation ; Stokes radiation ; kinetics ; spectrum ; distribution function
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract Statistical properties of the Raman scattering of an intense step pulse are investigated by numerical solution of the equations of a semi-classical theory with assignment of a random Gaussian distribution of the initial polarization over the sample. The probability density functions of the intensity, energy, delay time, and width of a Stokes pulse and also of the position, height, and width of the spectral peaks of the first incidental Stokes component with the preservation of the phase memory of scattering centers are calculated. The influence of collisional dephasing on the fluctuation of these characteristics is considered.
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  • 59
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    Powder metallurgy and metal ceramics 39 (2000), S. 540-544 
    ISSN: 1573-9066
    Keywords: compaction ; facing ; cumulative charge ; powder ; composite ; heterogeneous structure ; particle ; kinetics ; surface ; die ; model ; xeroradiogram
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract An experimental and numerical (finite element method) study is carried out for the effect of forming scheme on property distribution for cumulative charge facings made from composite heterogeneous powder material. An experimental procedure is developed for studying powder particle flow kinetics. It is shown that use of composite punches and partition of the moulded material into a number of sub-divisions with their successive compaction achieves a more uniform density distribution for an article. It is demonstrated how the direction of the force of friction on the die walls during compaction affects the compaction of articles with faces that are not perpendicular to the direction of the pressing. The results obtained make it possible to select the optimum compaction regime taking account of production features connected with powder material composition as well as service characteristics.
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  • 60
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    Pharmaceutical research 17 (2000), S. 701-706 
    ISSN: 1573-904X
    Keywords: vapor sorption ; molar heat of adsorption ; kinetics ; isothermal microcalorimetry ; recrystallization ; hydration
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Purpose. In this study, instrumentation for measuring vapor sorptionenthalpies and sorption uptakes simultaneously with an isothermalmicrocalorimeter is introduced. Various pharmaceutical modelsubstances undergoing phase transitions when exposed to humid conditions(25°C), were employed to evaluate the usefulness and sensitivity ofthe constructed experimental method. Methods. The sample is placed in the sample vessel of a RH cell andthe moisture content of the air flow is controlled. From the RH cellthe air flow is conducted into a subsequent perfusion cell in which asaturated salt solution has been loaded. The RH cell and perfusioncells are positioned in the sample sides of two twin calorimetric units.Depending on the moisture content in the outlet flow leaving thepreceding RH cell, the heat flow signal from the subsequent perfusioncell will vary. By means of blank measurement with identical settings,the rate of water sorption can be calculated and, by integration, theamount of sorbed water is obtained. Results. Amorphous lactose and cefadroxil undergo recrystallizationwhen the moisture level in the surroundings exceeds the thresholdvalues specific to each compound. During the sorption phase, heat isevolved fairly linearly as a function of consumed moisture, and alsoafter the recrystallization, the heats indicate linear behavior. The heatvalues for the desorption phase of amorphous lactose and the adsorptionof crystalline lactose coincide. With the different anhydrous forms oftheophylline, the hydration takes place more rapidly in the metastableform I, and generally, the process is more energetic in form I. In allcases, the gravimetric results agree with the water sorption uptakescalculated from the calorimetric data. Conclusions. The technique introduced offers a rapid and sensitivemethod to gain new insights into the transitions in which vapors areinvolved. In addition, different kinds of surfaces with various energeticscan now be studied more closely.
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  • 61
    ISSN: 1573-515X
    Keywords: gaseous ; kinetics ; mercury ; methods ; speciation ; waters
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Mercury evasion from water is commonly modeled using measurements of dissolved gaseous mercury (DGM). We developed a method using a recently available automated field-ready mercury vapor analyzer to rapidly measure the concentrations of DGM in surface waters. We summarize here results of laboratory tests of the method, field intercomparisons with a manual method, and selected data from recent sampling campaigns in Florida and Michigan. The method uses the 1.5 lpm flow of a Tekran® Model 2537A mercury analyzer to purge and analyze discrete water samples, generating near real time (5-min) data on DGM in samples and blanks. Application of the Tekran allowed for detailed analysis of DGM removal kinetics and short-term diel studies characterizing the influence of sunlight and precipitation on DGM production in surface waters. Gas removal kinetics for dozens of samples indicates a first-order rate constant, and supports a 20-min. purge time for surface water samples from Florida (40-min for Michigan samples). Blanks are measured during a second such purge. Our results indicate that DGMs determined by both automated and manual methods are generally comparable, and that DGM in Florida samples is unstable during storage (loss rate constant ∼0.1--0.2 h-1), probably due to oxidation. This suggests that rapid in-field analysis is preferred to storage with delayed analysis. Our data indicate that DGM at the Florida site is influenced by inputs of reactive Hg in rainwater, and by production of surface DGM during photoreduction of oxidized Hg in the water column.
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  • 62
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    Genetica 108 (2000), S. 229-237 
    ISSN: 1573-6857
    Keywords: autoregulation ; dimerization ; kinetics ; post-transcriptional regulation ; transposable elements (TEs)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Kinetic modeling of the self-regulatory mechanisms of transposable elements (TEs) involving interactions of one or a few gene products makes predictions that are often at odds with observed results. In particular, explanations of TE autorepression at high copy number that invoke a decrease in number of active monomers through dimerization, amyloidization, and protein-mRNA binding to create an inactive state are not supported by analysis of the corresponding kinetic models. This is also true for similar mRNA–mRNA binding models. Self-repression in marineras well as other TEs can, however, be explained by a host-independent model in which inactive dimers compete with monomers for TE binding sites at the ends of the element. This model would also allow heterodimer poisoning to down-regulate transposition in the presence of divergent nonautonomous elements, since nondivergent monomers would be required at both TE ends for transposition.
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  • 63
    ISSN: 1573-6881
    Keywords: Permeability transition ; ADP/ATP translocase ; kinetics ; adenosine diphosphate ; carboxya tractyloside ; bongkekic acid ; mitochondria
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology , Physics
    Notes: Abstract Low levels of ADP binding at the ADP/ATP translocase caused inhibition of the Ca2+-inducedpermeability transition of the mitochondrial inner membrane, when measured using the shrinkage assay on mitochondria, which have already undergone a transition. Inhibition was preventedby carboxyatractyloside, but potentiated by bongkrekic acid, which increased the affinity forinhibition by ADP. This suggests that inhibition was related to the conformation of thetranslocase. Ca2+ addition was calculated to remove most of the free ADP. Ca2+ added after ADPinduced a slow decay of the inhibition, which probably reflected the dissociation of ADP fromthe translocator. We conclude that the probability of forming a permeability transition pore(PTP) is much greater when the translocase is in the CAT conformation than in the BKAconformation, and, in the absence of CAT and BKA, the translocator is shifted between theBKA and CAT conformations by ADP binding and removal, even in deenergized mitochondria with no nucleotide gradients.
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  • 64
    ISSN: 1573-2614
    Keywords: Neuromuscular relaxants ; rocuronium ; kinetics ; distribution
    Source: Springer Online Journal Archives 1860-2000
    Topics: Computer Science , Medicine
    Notes: Abstract Objective.To determine the relationship between the rate ofrocuronium injection and the onset time of neuromuscular block. Methods.After intravenous induction, 60 female patients (ASA I–II) wereassigned randomly into 3 groups for rocuronium administration within1–15, 15–30 or 30–60 seconds. Acceleromyography of the thumbwas performed using train-of-four (TOF) stimulation. Times to 50% and 90%twitch depression of the first twitch of the TOF stimulation (T1) wererecorded. Results.Injection time significantly influences time to 50%relaxation, but not time to 90% relaxation. Body mass index is negativelycorrelated with time to 50% and 90% relaxation. Conclusions.Weconclude that rate of injection influences only the initial phase ofdevelopment of the block and that slower injection times do not significantlyaffect time to 90% relaxation at the adductor pollicis muscle.
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  • 65
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    Journal of clinical monitoring and computing 16 (2000), S. 351-360 
    ISSN: 1573-2614
    Keywords: carbon dioxide ; oxygen ; kinetics ; non-steady state ; cardiac output ; PEEP ; pulmonary embolism ; pulmonary gas exchange monitoring
    Source: Springer Online Journal Archives 1860-2000
    Topics: Computer Science , Medicine
    Notes: Abstract Traditionally, the study of CO2 and O2 kinetics in the body has been mostly confined to equilibrium conditions. However, the peri-anesthesia period and the critical care arena often involve conditions of non-steady state. The detection and explanation of CO2 kinetics during non-steady state pathophysiology have required the development of new methodologies, including the CO2 expirogram, average alveolar expired PCO2, and CO2 volume exhaled per breath. Several clinically relevant examples of non-steady state CO2 kinetics perturbations are examined, including abrupt decrease in cardiac output, application of positive end-expiratory pressure during mechanical ventilation, and occurrence of pulmonary embolism. The lesser known area of non-steady state O2 kinetics is introduced, including the measurement of pulmonary O2 uptake per breath. Future directions include the study of the respiratory quotient per breath, where the anaerobic threshold during anesthesia is identified by increasing respiratory quotient.
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  • 66
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    Water resources management 14 (2000), S. 417-434 
    ISSN: 1573-1650
    Keywords: adsorption ; feldspar ; industrial effluent ; pollution control ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Architecture, Civil Engineering, Surveying , Geography
    Notes: Abstract Feldspar, among many natural substances such as termitemount-clay, saw-dust, kaolinite and dolomite, offers asignificant removal ability for sulfate, phosphate, and coloredsubstances. Optimization of experimental parameters such assolution pH and flow rate reveals, that the maximum efficiency forremoval of phosphate, sulfate, and colored substances is about42, 52, and 73% respectively. X-ray diffraction, adsorptionisotherm and recovery studies suggest, that the removal processof anions occurs via ion exchange in conjunction with surfaceadsorption. Furthermore, reaction rate studies indicate thatthe removal of the selected pollutants by feldspar follows first-order kinetics. Although the percent removal, under the optimized conditions, is higher for laboratory prepared solutions, efficiency is a little less for industrial effluentsdue to interferent effects.
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    Journal of thermal analysis and calorimetry 62 (2000), S. 353-363 
    ISSN: 1572-8943
    Keywords: controlled environment ; high-T c superconductors ; kinetics ; microgravimetric investigations
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Many properties of oxide superconductors depend on the oxygen concentration and its distribution in the samples. The microgravimetric method is very useful to study of oxide superconductors, as it allows investigations in vacuum and controlled environments in classical applications: thermogravimetric analysis for the study of solid-state reactions, determinations of oxygen contents in redox reactions and the combined measurement of mass and additional parameters, e.g. evolved gas analysis etc. Single-phase samples of high-temperature superconductors were synthesized from stoichiometric mixtures of high-purity oxides and carbonates. Appropriate amounts of the precursor powders were homogenized manually or by a mechanical ball mill and subsequently calcined at temperatures in the 800 to 950°C range with intermediate grinding to ensure homogenous reaction. The lattice parameters of all preparations were controlled, in both initial and final experiments, by the X-ray powder method (CuKα radiation), using a Stadi P (Stoe) diffractometer with a position-sensitive detector. It is well known that temperature and mass can be measured with an accuracy higher by orders of magnitude than it is still possible for the thermoanalyst to determine the transformation temperatures or the mass changes due to overlapping partial reactions. Applications of Cahn microbalance to study of high-temperature superconductors are presented.
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  • 68
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    Journal of thermal analysis and calorimetry 62 (2000), S. 747-755 
    ISSN: 1572-8943
    Keywords: benzoic acid ; europium complex ; kinetics ; non-isothermal ; thermal decomposition
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The thermal decomposition of Eu2(BA)6(bipy)2 (BA=C2H5N– 2, benzoate; bipy=C10H8N2, 2,2'-bipyridine)and its kinetics were studied under the non-isothermal condition by TG-DTG, IR and SEM methods. The kinetic parameters were obtained from analysis of the TG-DTG curves by the Achar method, the Madhusudanan-Krishnan-Ninan (MKN) method, the Ozawa method and the Kissinger method. The most probable mechanism function was suggested by comparing the kinetic parameters. The kinetic equation for the first stage can be expressed as: dα/dt=Aexp(–E/RT)3(1–α)2/3.
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  • 69
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    Journal of thermal analysis and calorimetry 63 (2000), S. 397-413 
    ISSN: 1572-8943
    Keywords: Cu–5 at%Zn ; DSC ; F.C.C. (Face Centered Cubic) ; kinetics ; short-range-order ; solute-vacancy complexes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A modified first order kinetic law, which describes the roles of bound and unbound vacancies, is proposed in order to predict defect decay and short-range-order kinetics of quenched binary alloys during linear heating experiments. The model has been applied to differential scanning calorimetry (DSC) curves of Cu–5 at%Zn quenched from different temperatures. Activation energy for migration of solute-vacancy complexes was also assessed from the kinetics of short-range-order using DSC traces. A value of 89.5±0.32 kJ mol–1 was obtained. The relative contribution of bound and unbound vacancies to the ordering process as influenced by quenching temperature was determined. In conjunction, a parametric study of the initial total defect concentration and effective energy for defect migration was performed in order to envisage their influence on the calculated DSC profiles.
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  • 70
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    Journal of thermal analysis and calorimetry 60 (2000), S. 25-33 
    ISSN: 1572-8943
    Keywords: DSC ; kinetics ; thermal decomposition ; 2,4,6-trinitrotoluene
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract An autocatalytic model involving the limited solubility of volatile catalytic products was applied to the thermal decomposition of 2,4,6-trinitrotoluene. The critical supersaturation of the thermal decomposition products with the catalytic properties was higher at a low heating rate. Decrease of the sample mass led to an increased critical supersaturation of the decomposition products. This is probably a result of the greater contribution of products adsorption on the aluminium pan surface. It is presumed that the differences observed in the rate constant are connected with the uncontrolled critical supersaturation of the volatile thermal decomposition products.
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  • 71
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    Structural chemistry 11 (2000), S. 341-346 
    ISSN: 1572-9001
    Keywords: Positronium chemistry ; kinetics ; spin-exchange reactions ; high- and low-spin 3d complexes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Continuing in our work on the correlations between the rate constants, k CR, of the ortho into para-positronium conversion reactions, CR, promoted by complexes of various 3d ions and the metal electron delocalization β caused by the ligands, the relationship between the parameters of the correlation lines pertinent to highand low-spin complexes of CrII, MnII, and CoII ions was ascertained. Moreover, it was experimentally verified, for the first time, that the statistical probability of the CR promoted by paramagnetic compounds with S = 1/2 is three times larger than that of the CR caused by compounds with S 〉 1/2.
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  • 72
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    Hyperfine interactions 128 (2000), S. 481-493 
    ISSN: 1572-9540
    Keywords: muon catalyzed fusion ; triple mixture ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract In this paper, we solve numerically kinetic equations for the chain reactions of μCF in triple H/D/T mixture. Regarding the computational results, we show that μCF efficiency decreases by adding hydrogen H to D/T mixture. This is in contradiction to the usual belief which expects the increase of μCF efficiency in H/D/T mixture. Our results are confirmed by the first and recent experiment on μdt cycling rate in the triple mixture.
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  • 73
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    Reaction kinetics and catalysis letters 69 (2000), S. 169-176 
    ISSN: 1588-2837
    Keywords: Al3+-exchanged pillared clay catalyst ; 2-methoxyethanol ; esterification ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The pillared clay catalyst, which was obtained by exposing activated clay powder to sulfuric acid and aluminium salts and calcining in air at 373 – 673 K, was found to be highly active for the title reaction. The activity is mainly attributed to the Lewis acid sites and also to a small number of Brönsted acid sites, whose number and strength increases with the extent of pillaring. The kinetic equation of surface esterification is y = 2.57x - 1.47.
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  • 74
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    Reaction kinetics and catalysis letters 70 (2000), S. 119-124 
    ISSN: 1588-2837
    Keywords: Tenoxicam ; photodegradation ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Photodegradation of tenoxicam was investigated under different reaction conditions. After 60 min of exposure to UV light, the photodegradation was extensive, and the maximum and minimum in the UV-visible spectrum were shifted to shorter and longer wavelengths, respectively. Ethanol exerted a photostabilizing effect on tenoxicam. Tenoxicam is more stable in acidic and basic media than in neutral solution. Increasing light intensity or temperature causes an increase in the rate of photodegradation. The photodegradation of tenoxicam was found to follow first-order kinetics under all these conditions.
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  • 75
    ISSN: 1588-2837
    Keywords: Ferrites ; aniline alkylation ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Kinetic parameters such as the activation energy (Ea) and Arrhenius frequency factor (A) for the N-methylation of aniline using methanol over Zn-Co ferrites have been calculated. The Ea value is found to be lower than the existing best alkylating systems such as γ-alumina and magnesium oxide.
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  • 76
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    Reaction kinetics and catalysis letters 71 (2000), S. 343-347 
    ISSN: 1588-2837
    Keywords: Deoximination ; chromium (VI) ; kinetics ; mechanism
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Oxidative deoximination of aldoximes and ketoximes by pyridium fluorochromate proceeds by nucleophilic attack of the chromate oxygen on the oxime carbon to give a cyclic intermediate in the rate-determining step.
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  • 77
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    Reaction kinetics and catalysis letters 70 (2000), S. 147-151 
    ISSN: 1588-2837
    Keywords: Oxo-functionalization ; [RuIII(amp)(pic)(H2O)] ; t-BuOOH ; kinetics ; cyclohexane cyclohexene ; toluene
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A novel mixed-ligand [RuIII(amp)(pic)(H2O)] complex (1) (H2amp = N-(hydroxyphenyl)salicyldimine; pic = picolinate) has been synthesized and characterized by physico-chemical methods. Complex 1has been found to be an effective catalyst in oxo-functionalization of C-H bond of organic substrates by using tert-butyl hydroperoxide (t-BuOOH) as a terminal oxidant. Formation of a high valent Ru(V)-oxo species as catalytic intermediate is proposed to be the source of oxygen atom in the oxidised product.
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  • 78
    ISSN: 1588-2837
    Keywords: Fe(CN)5(4-tbupy)3- ; kinetics ; electrolytes ; substitution
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The ligand substitution reaction [Fe(CN)5(4-tbupy)]3- + pyrazine (4-tbupy=4-tertbutylpyridine) was studied in aqueous concentrated electrolyte solutions at 298 K. Plots of ln(k/kw) against (γ-γw), where the subscript w refers to pure water and γ is the surface tension of the appropriate salt solution, gave a common straight line for all the electrolytes studied and permits to estimate the activation volume.
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  • 79
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    Reaction kinetics and catalysis letters 69 (2000), S. 39-46 
    ISSN: 1588-2837
    Keywords: Coke formation ; kinetics ; USHY zeolites ; ethene ; propene ; 1-butene
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A simplified three-parameter model for the interpretation of the kinetic data of coke formation during transformation of light olefins is presented. This model has been applied to the transformation of ethene, propene and 1-butene over fresh and regenerated zeolite USHY at 623 K. The proposed model covers both the coverage of the acid sites and the autocatalytic growth of coke.
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  • 80
    ISSN: 1588-2837
    Keywords: Dichlorocyclopropanation ; 4-vinyl-1-cyclohexene ; phase transfer catalysis ; kinetics
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of regioselective dichlorocyclopropanation of 4-vinyl-1-cyclohexene has been studied under controlled phase transfer catalysis conditions, using aqueous sodium hydroxide as the base and 2-benzylidine-N,N,N,N′,N′,N′-hexaethylpropane-1,3-diammonium dibromide (Dq-Br) as a new phase transfer reagent. The reaction was carried out at 40 °C under pseudo-first order conditions by employing aqueous sodium hydroxide and chloroform in excess and was monitored by gas chromatography. The effect of various experimental parameters on the rate of the reaction has been studied and based on the experimental results, a suitable mechanism is proposed.
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  • 81
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    Reaction kinetics and catalysis letters 69 (2000), S. 247-252 
    ISSN: 1588-2837
    Keywords: Phosphorous acid ; oxidation ; kinetics ; mechanism
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The oxidation of lower phosphorus oxyacids by benzyltrimethylammonium chlorobromate (BTMACB) proceeds by a mechanism involving a hydride-ion transfer from oxyacids to the oxidant in the rate-determining step.
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  • 82
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    Reaction kinetics and catalysis letters 70 (2000), S. 139-145 
    ISSN: 1588-2837
    Keywords: Oxidation of sulfides ; kinetics ; Ni-oxide system ; reaction mechanism
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Catalytic oxidation of sulfide ions in aqueous solutions by air oxygen has been investigated using a Ni-oxide system as a catalyst. The kinetics and the selectivity of the oxidation process were studied by varying the pH, catalyst amount and reaction temperature. A reduction/oxidation mechanism of the reaction has been supposed comprising interaction between the surface active oxygen of the catalyst and HS− and reoxidizing of the reduced catalyst by the dissolved oxygen. The results obtained show that the Ni-oxide system is a promising catalyst for practical application.
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  • 83
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    Reaction kinetics and catalysis letters 70 (2000), S. 235-241 
    ISSN: 1588-2837
    Keywords: Methanol ; isobutanol ; ethers ; γ-Al2O3 ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetic of methanol (MeOH) and isobutanol (iBuOH) coupling to ethers has been studied. Catalytic tests were carried out in the gas phase in a fixed-bed flow microreactor, in the temperature range of 463-533 K, under atmospheric pressure, using γ-Al2O3 as the catalyst. The quasi-homogeneous model for the process was assumed. The reaction rates were described by simple kinetics.
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    Reaction kinetics and catalysis letters 70 (2000), S. 319-324 
    ISSN: 1588-2837
    Keywords: Atmospheric chemistry ; kinetics ; OH-radical ; CH2F2
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The rate constant value of k 1 = (6.05 ± 0.20)×109 cm3 mol−1 s−1 (with ± 1σ error) has been determined for the reaction OH + CH2F2 (1) by applying the discharge-flow/resonance-fluorescence method at 298 K.
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    Reaction kinetics and catalysis letters 71 (2000), S. 47-54 
    ISSN: 1588-2837
    Keywords: Alkylbenzenes ; hydrogenation ; nickel ; kinetics ; stereochemistry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Experimental data on gas-phase hydrogenation of several alkylbenzenes (toluene, ethlylbenzene, o-, m-, p-xylenes, mesitylene) over nickel catalyst are summarized. Rate dependence as a function of the chemical nature of substituent and position in the aromatic ring is discussed. The stereochemical distribution for dialkylbenzene and trialkylbenzene is addressed.
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    Reaction kinetics and catalysis letters 71 (2000), S. 295-300 
    ISSN: 1588-2837
    Keywords: Sintering ; kinetics ; Pt/Al2O3
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The variation of dispersion of Pt on Al2O3 support with sintering time is measured and the value of equilibrium dispersion of Pt is obtained directly. It is found that a General Power Law Expression can fit the experimental data well.
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  • 87
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    World journal of microbiology and biotechnology 16 (2000), S. 601-605 
    ISSN: 1573-0972
    Keywords: Growth phases identification ; kinetics ; Rhizopus oryzae ; solid-state fermentation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract A general equation correlating the variation rate of the fermenting medium weight (dry matter) and the cell biomass growth rate in solid-state fermentation tests is proposed with the main purpose of identifying the microbial growth phases.
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  • 88
    ISSN: 1573-2746
    Keywords: 8-hydroxyquinaldine ; electropolymerization ; adsorption ; glassy carbon ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Abstract The kinetics and thermodynamics of the electropolymerization of the chelating agent 8-hydroxyquinaldine on GCE's (Glassy Carbon Electrodes') surface from aqueous phosphate buffers are reported. Thermodynamic functions related to the adsorption of the monomer on the GCE's surfaces were determinated. No contribution from GCE surface's functional group to the electropolymerization reactions was reported. The effects of monomer concentration, pH, and temperature on the electrochemical growth of poly 8-hydroxyquinaldine were investigated. The results suggest that the propagation of the electropolymerization process takes place via a free radical chain reactions. Furthermore, the results indicate that the electrochemical growth of the polymeric films is dictated by pre-polymerization adsorption on the electrode surface.
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  • 89
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    Chemistry of heterocyclic compounds 36 (2000), S. 857-861 
    ISSN: 1573-8353
    Keywords: salts of 2,5-dimercapto-1,3,4-thiadiazole ; alkylation ; kinetics ; electronic absorption spectra
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A kinetic investigation has been carried out, using electronic absorption spectra, of the alkylation with benzyl chloride of the dihydrazine, monohydrazine, and the disodium salts of 2,5-dimercapto-1,3,4-thiadiazole, and also of the hydrazine and sodium salts of 5-benzylthio-2-mercapto-1,3,4-thiadiazole. The rates orders and constants were established for the benzylation reaction and it was noted that the reaction rate depends on the cation of these salts and the degree of substitution of the 2,5-dimercapto-1,3,4-thiadiazole.
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    Journal of applied electrochemistry 29 (1999), S. 191-200 
    ISSN: 1572-8838
    Keywords: cyclic redox reaction ; dissolution ; kinetics ; manganese dioxide ; mechanism ; pyrite
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract This paper describes a study of the kinetics and mechanism of MnO2 dissolution in H2SO4 in the presence of pyrite through leaching and electrochemical parameters. Manganese(iv) was found to dissolve mainly through reduction by the ferrous ion generated during oxidation of pyrite by the ferric ion. The oxidation which is slower and rate controlling may proceed through two different reactions, one producing S0 and the other SO42−. Manganese dissolution runs at the same rate as that of pyrite oxidation by maintaining ferrous ion concentration at a much lower level than that of ferric. Kinetic equations based on corrosion coupling principles are developed to explain the observed leaching behaviour.
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  • 91
    ISSN: 1572-8773
    Keywords: acidophilic ; strain ; oxidation ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract Recovery of metal values from sulfide ores by use of acidophilic microorganisms is gaining importance. A number of commercial/pilot plants are setup to find out the techno-economic feasibility of the overall process. The main drawback in the process is the slow kinetics of dissolution of metal values from the sulfide ores. To make the technology e attractive the kinetics should be improved considerably. There are various factors which determine the overall kinetics such as bacterial activity and concentration, iron and sulfur oxidation, oxygen consumption, reactor design and nature of ore. A brief review has been made dealing with the above parameters
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  • 92
    ISSN: 1572-8900
    Keywords: Cellulose ; alkaline degradation ; peeling off ; degree of polymerization ; kinetics ; (gluco)isosaccharinic acid
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Energy, Environment Protection, Nuclear Power Engineering , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The degradation of cellulosic materials, differing mainly in the degree of polymerization and the number of reducing end groups, was studied under the alkaline conditions similar to those existing in a cementitious repository for low- and intermediate-level radioactive waste (pH 13.3, T = 25°C). The kinetics of alkaline degradation (peeling-off reaction) were studied and the data analyzed by the model of Haas et al. [13]. The observed kinetic parameters for the propagation reaction and overall stopping reaction were compared with literature data. Although measured under different experimental conditions, literature data and data from this study show a consistent picture. Differences in the extent of degradation observed for the different cellulosic materials could be satisfactorily explained by differences in reducing end group content and, consequently, by differences in the degrees of polymerization. Besides the number of reducing end groups, the degree of amorphousness also plays an important role. The main degradation products formed under the experimental conditions used are α- and β-(gluco)isosaccharinic acid. This is in agreement with many other studies on alkaline degradation of cellulose. The two isomers are formed in roughly equal amounts.
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  • 93
    ISSN: 1572-8757
    Keywords: micropore size distribution ; activated carbon ; adsorption ; desorption ; equilibrium ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract This paper deals with the prediction of adsorption equilibrium and kinetics of hydrocarbons onto activated carbon samples having different micropore size distribution (MPSD). The microporous structure of activated carbon is characterised by the distribution of slit-shaped micropores, which is assumed to be the sole source of surface heterogeneity. The interaction between adsorbate molecule and pore walls is described by the Lennard-Jones potential theory. Different adsorbates have access to different pore size range of activated carbon due to the size exclusion, a phenomenon could have a significant influence on both multicomponent equilibria and kinetics. Activated carbons with three different MPSDs are studied with ethane and propane as the two model adsorbates. The Heterogeneous Macropore Surface Diffusion model (HMSD) is employed to simulate adsorption kinetics. The simulation results show that the MPSD is an important factor affecting both the multicomponent equilibria and kinetics.
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    Catalysis letters 60 (1999), S. 51-57 
    ISSN: 1572-879X
    Keywords: furfural hydrogenation ; Cu/carbon catalysts ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Furfural hydrogenation over copper dispersed on three forms of carbon – activated carbon, diamond and graphitized fibers – were studied. Only hydrogenation of the C=O bond to form either furfuryl alcohol or 2‐methyl furan occurred at temperatures from 473 to 573 K. Reduction at 573 K gave the most active catalysts, all three catalysts had activation energies of 16 kcal/mol, and turnover frequencies were 0.018–0.032 s-1 based on the number of Cu0 + Cu+ sites, which were counted by N2O adsorption at 363 K and CO adsorption at 300 K, respectively. The Cu/activated carbon catalyst showed no deactivation during 10 h on stream, in contrast to the other two catalysts. A simple Langmuir–Hinshelwood model invoking two types of sites was able to fit all kinetic data quite satisfactorily, thus it was consistent with the presence of both Cu0 and Cu+ sites.
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    Catalysis letters 60 (1999), S. 167-171 
    ISSN: 1572-879X
    Keywords: ammonia decomposition ; iron catalyst ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The decomposition of ammonia is a reaction associated with the process of the nitriding of metals. The kinetics of the ammonia decomposition on iron catalysts has been studied using a differential reactor with internal mixing. The balance between the inlet and outlet ammonia quantity has been used to determine the degree of conversion. The rate of ammonia decomposition could be described by the following expression: r = k0 exp (Ea/RT)pNH3. The activation energy of the ammonia decomposition process has been found for samples with potassium as E a= 96 kJ/mol, for samples without potassium as E a= 87 kJ/mol.
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  • 96
    ISSN: 1572-8757
    Keywords: kinetics ; isotope-exchange ; nitrogen ; adsorption ; methane ; zeolite ; equilibria
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract The Isotope Exchange Technique (IET) was used to simultaneously measure pure and binary gas adsorption equilibria and kinetics (self-diffusivities) of CH4 and N2 on pelletized 4A zeolite. The experiment was carried out isothermally without disturbing the adsorbed phase. CH4 was selectively adsorbed over N2 by the zeolite because of its higher polarizability. The multi-site Langmuir model described the pure gas and binary adsorption equilibria fairly well at three different temperatures. The selectivity of adsorption of CH4 over N2 increased with increasing pressure at constant gas phase composition and temperature. This curious behavior was caused by the differences in the sizes of the adsorbates. The diffusion of CH4 and N2 into the zeolite was an activated process and the Fickian diffusion model described the uptake of both pure gases and their mixtures. The self-diffusivity of N2 was an order of magnitude larger than that for CH4. The pure gas self-diffusivities for both components were constants over a large range of surface coverages (0 〈 θ 〈 0.5). The self-diffusivities of CH4 and N2 from their binary mixtures were not affected by the presence of each other, compared to their pure gas self-diffusivities at identical surface coverages.
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  • 97
    ISSN: 1572-879X
    Keywords: hydrogen ; desorption ; copper ; activation energy ; kinetics ; order of desorption
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of desorption of hydrogen from the copper component of an alumina-supported polycrystalline copper catalyst has been studied in detail by temperature-programmed desorption (TPD). Line-shape analysis of the hydrogen TPD spectra shows: (i) that the desorption is second order, (ii) that the desorption activation energy is in the range 64–68 kJ mol−1 in the coverage range 7–44% of a monolayer, and (iii) that the desorption pre-exponential term has a value ∼10−5 cm2 s−1 atom−1 consistent with the desorption being second order, involving mobile adsorbates and a mobile desorption transition state.
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    Bulletin of volcanology 61 (1999), S. 121-137 
    ISSN: 1432-0819
    Keywords: Key words Vulcano ; Aeolian islands ; Landslide ; Tsunami ; Finite-element technique ; Lagrangian approach ; Numerical simulations
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences
    Notes: Abstract  On 20 April 1988 a landslide of approximately 200,000 m3 occurred on the northeastern flank of the volcano La Fossa on the island of Vulcano. The landslide fell into the sea, producing a small tsunami in the bay between Punte Nere and Punta Luccia that was observed locally in the neighbouring harbour called Porto Levante. The slide occurred during a period of unrest at the volcano that was monitored very accurately. The study of this event is composed of two parts, the simulation of the landslide and the simulation of the ensuing tsunami; the former is studied by means of a Lagrangian-type numerical model in which the landslide is seen as a multibody system, an ensemble of material-deforming blocks interacting together during their motion; the latter is simulated according to the Eulerian view by solving the shallow-water approximation to Navier-Stokes equations of fluid dynamics, with the incorporation of a forcing term depending on the slide motion. Technically, the slide evolution is computed first, and this result is then used to evaluate the excitation term of the hydraulic equations and to calculate the tsunami propagation. Computed wave fronts radiate both toward the open sea, with rapid amplitude decay, and along the shore, in the form of edge waves that lose energy slowly. Comparison between model outputs and observations can be carried out only in a qualitative way owing to the absence of tide-gauge records, and results are satisfactory.
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  • 99
    Electronic Resource
    Electronic Resource
    Springer
    Journal of statistical physics 95 (1999), S. 23-43 
    ISSN: 1572-9613
    Keywords: model alloy ; Monte Carlo ; elastic interactions ; phase separation ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract We study via Monte Carlo simulations the influence of elastic interactions on the ordering and decomposition of a two-dimensional model binary alloy with antiferromagnetic nearest and ferromagnetic next nearest neighbor type interactions following a quench into the coexistence region. The elastic interaction leads to the development of a platelet morphology for the segregated ordered and disordered regions. A length scale characterizing the coarsening process follows a law of the type R=a+bt 1/3 with the growth b decreasing with the amount of ordered phase; this appears to be due to the presence of anti-phase boundaries between neighboring domains ordered on different sublattices which are difficult to eliminate. The application of uniaxial external stress results in “rafting” of the domains. Many of the simulation results are in agreement with experimentally observed effects in nickel-base superalloys.
    Type of Medium: Electronic Resource
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  • 100
    Electronic Resource
    Electronic Resource
    Springer
    Journal of thermal analysis and calorimetry 55 (1999), S. 9-19 
    ISSN: 1572-8943
    Keywords: ARC ; DSC ; HFC ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Isopropylnitrate (IPN) is described as a detonable material used in propellants and explosives. While there is considerable information available on its sensitivity and compatibility with other materials, very little is known about its thermochemical properties. This paper will describe the results obtained from some DSC, heat flux calorimetry (HFC) and accelerating rate calorimetry (ARC) measurements. The ASTM DSC method using a hermetic aluminum pan having a lid with a laser-produced pin hole was used to determine the vapour pressure of IPN1. Results calculated from an Antoine equation are in substantial agreement with those determined from DSC measurements. From the latter measurements, the enthalpy of vaporization was determined to be 35.32±0.62 kJ mol−1. Attempts to determine vapour pressures above about 0.8 MPa resulted in significant decomposition of IPNg. The enthalpy change for decomposition in sealed glass systems was found to be -3.43±0.09 kJ g−1 and -3.85±0.03 kJ g−1, respectively from DSC and HFC measurements on IPN1 samples loaded in air. Slightly larger exotherms were observed for the HFC results in air than those in inert gas, suggesting some oxidation occurs. In contrast, no significant difference in the observed onset temperature of about 150°C was observed for both the HFC and ARC results. From DSC measurements, an Arrhenius activation energy for decomposition of 126±4 kJ mol−1 was found. These measurements were also conducted in sealed glass systems and decomposition appeared to proceed primarily from the liquid phase.
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