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  • 1
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    Geochemistry of volcanic fluids : A special issue of the Bulletin of Volcanology in honour of Yuri A. Taran (2011)
    Springer
    Details
    Publication Date: 2021-05-17
    Description: This special issue is dedicated to Yuri Taran's outstanding contributions to gas geochemistry that began in the early 1980s with his work on deuterium and 18O compositions of geothermal waters in the Mutnovsky (Kamchatka) region and continues to this day with work on the Kamchatka volcanic volatile budget, carbon isotopes of hydrocarbons, and new insights into the geochemistry of El Chichón volcano, Chiapas. Yuri has contributed greatly to the field of volcanic gas geochemistry and was the first to recognize the distinct deuterium and oxygen isotopic composition of fumarole condensates from volcanoes in Kamchatka (Taran et al. 1987a). The shift in δD and δ18O to significantly heavier values compared to local meteoric water led Yuri to introduce the term “andesitic water” (Taran et al. 1989a, b) which has since been recognized at subduction zone volcanoes globally. This distinct isotopic composition is evidence that volcanoes release water that ultimately originates as subducted seawater and is recycled through the mantle wedge back to the earth's surface. Yuri's early work on the gas emissions from Kamchatka and Kurile Islands volcanoes also included the development and testing of gas geothermometers (Taran 1986) and investigating hydrothermal alteration using isotopic data (Taran et al. 1987b). His curiosity remained focused on the isotope systematics of volcanic gases discharging from Kamchatka and the Kuriles through the late 1980s and 1990s with publications on the gas compositions of Klyuchevskoi (Taran et al. 1991), Mutnovsky (Taran et al. 1992), Avachinsky and Koryaksky (Taran et al. 1997). Yuri was involved in the discovery of a pure and unique rhenium mineral on Kudryavy volcano (Korzhinsky et al. 1994) and provided one of the most detailed chemical studies of high temperature (up to 950°C) fumaroles to date of any volcano (Taran et al. 1995). His 1995 paper on Kudryavy remains highly cited and provides the highest quality volcanic gas data which also include trace elements from a subduction zone. Such data are crucial when we attempt to interpret lower temperature volcanic gas compositions or calculate rare metal fluxes from volcanoes worldwide. His most recent publication on Kamchatka-Kurile volcanic emissions provides a detailed analysis of the total gas flux from these volcanoes (Taran 2009).
    Description: Published
    Description: 369-371
    Description: 1.2. TTC - Sorveglianza geochimica delle aree vulcaniche attive
    Description: 2.4. TTC - Laboratori di geochimica dei fluidi
    Description: JCR Journal
    Description: reserved
    Keywords: Fluids Geochemistry ; 04. Solid Earth::04.04. Geology::04.04.12. Fluid Geochemistry ; 04. Solid Earth::04.08. Volcanology::04.08.06. Volcano monitoring
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 2
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    Time-resolved seismic tomography detects magma intrusions at Mt. Etna (2007)
    American Association for the Advancement of Science
    Details
    Publication Date: 2017-04-04
    Description: The continuous volcanic and seismic activity at Mount Etna makes this volcano an important laboratory for seismological and geophysical studies. We used repeated three-dimensional tomography to detect variations in elastic parameters during different volcanic cycles, before and during the October 2002–January 2003 flank eruption. Well-defined anomalous low P- to S-wave velocity ratio volumes were revealed. Absent during the pre-eruptive period, the anomalies trace the intrusion of volatile-rich (Q4 weight percent) basaltic magma, most of which rose up only a few months before the onset of eruption. The observed time changes of velocity anomalies suggest that four-dimensional tomography provides a basis for more efficient volcano monitoring and shortand midterm eruption forecasting of explosive activity.
    Description: Published
    Description: 821-823
    Description: reserved
    Keywords: NONE ; 04. Solid Earth::04.01. Earth Interior::04.01.02. Geological and geophysical evidences of deep processes ; 04. Solid Earth::04.06. Seismology::04.06.07. Tomography and anisotropy ; 04. Solid Earth::04.08. Volcanology::04.08.06. Volcano monitoring
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 3
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    Lava effusion rate definition and measurement: a review (2007)
    Springer
    Details
    Publication Date: 2017-04-04
    Description: Measurement of effusion rate is a primary objective for studies that model lava flow and magma system dynamics, as well as for monitoring efforts during on-going eruptions. However, its exact definition remains a source of confusion, and problems occur when comparing volume flux values that are averaged over different time periods or spatial scales, or measured using different approaches. Thus our aims are to: (1) define effusion rate terminology; and (2) assess the various measurement methods and their results. We first distinguish between instantaneous effusion rate, and time-averaged discharge rate. Eruption rate is next defined as the total volume of lava emplaced since the beginning of the eruption divided by the time since the eruption began. The ultimate extension of this is mean output rate, this being the final volume of erupted lava divided by total eruption duration. Whether these values are total values, i.e. the flux feeding all flow units across the entire flow field, or local, i.e. the flux feeding a single active unit within a flow field across which many units are active, also needs to be specified. No approach is without its problems, and all can have large error (up to ∼50%). However, good agreement between diverse approaches shows that reliable estimates can be made if each approach is applied carefully and takes into account the caveats we detail here. There are three important factors to consider and state when measuring, giving or using an effusion rate. First, the time-period over which the value was averaged; second, whether the measurement applies to the entire active flow field, or a single lava flow within that field; and third, the measurement technique and its accompanying assumptions.
    Description: Published
    Description: 1-22
    Description: 1.5. TTC - Sorveglianza dell'attività eruttiva dei vulcani
    Description: JCR Journal
    Description: reserved
    Keywords: Lava ; Instantaneous effusion rate ; Time-averaged discharge rate ; Eruption rate ; Monitoring ; 04. Solid Earth::04.08. Volcanology::04.08.99. General or miscellaneous ; 04. Solid Earth::04.08. Volcanology::04.08.06. Volcano monitoring ; 04. Solid Earth::04.08. Volcanology::04.08.07. Instruments and techniques
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 4
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    Double origin of hydrothermal convective flux variations in the Fossa of Vulcano (Italy) (2007)
    Springer
    Details
    Publication Date: 2017-04-03
    Description: Soil-temperature measurements can provide information on the distribution of degassing fissures, their relationship to the internal structure of the volcano, and the temporal evolution of the system. At Vulcano Island (Italy) heat flux from a 〈3 km-deep magma body drives a hydrothermal system which extends across the main Fossa crater. This heat flux is also associated with variable magmatic gas flow. A high density map of soil-temperatures was made in 1996 at a constant depth of 30 cm on the central and southern inner flanks of the Fossa crater. These measurements extended over an area covering about 0.04 km2, across which the heat flux is predominantly associated with a shallow boiling aquifer. The map shows that hot zones relate to structures of higher permeability, mainly associated with a fissure system dating from the last eruptive cycle (1888-90). From 1996 to January 2005, we studied the evolution of the heat flux for the high temperature part of the map, both by repeating our measurements as part of fourteen visits, during which temperatures were measured at a constant depth, and using data from permanent stations which allowed soil-temperatures to be continuously measured for selected vertical profiles. These data allowed us to calculate the heat flux, and its variation, with good precision for values lower than about 100 W m-2, which is generally the case in the study area. Above 100 W m-2 although the heat flux value is underestimated its variations are recorded with an error less than 10%. During the period 1996-2004 two increases in the thermal flux were recorded. The first one was related to the seismic crisis of November 1998 which opened existing or new fissures. The second, in November 2004, was probably due to magma migration, and was associated with minor seismic activity.
    Description: Published
    Description: on line first
    Description: 1.2. TTC - Sorveglianza geochimica delle aree vulcaniche attive
    Description: JCR Journal
    Description: partially_open
    Keywords: hydrothermal flux ; soil temperature ; monitoring ; seismic activity ; Vulcano ; 04. Solid Earth::04.08. Volcanology::04.08.06. Volcano monitoring
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 5
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    A syn-eruptive ground deformation episode measured by GPS, during the 2001 eruption on the upper southern flank of Mt Etna (2005)
    Springer
    Details
    Publication Date: 2017-04-04
    Description: Ground deformation occurring on the southern flank of Mt Etna volcano during the JulyAugust 2001 eruption was monitored by GPS measurements along an EW profile crossing the fissure system. This profile was measured eight times during the eruption, using the 'stop and go' semi-kinematic technique. Horizontal and vertical displacements between GPS surveys are reported for each station. The most significant event is a deformation episode occurring during the first week of the eruption, between 2527 July. Displacements were measured on benchmarks close to the eruptive fissure and the tensile 1989 fracture. Data inversions for measured displacements were performed using the Okada model. The model shows the narrowing of the 2001 dyke accompanied by a dextral dislocation along an east-dipping fault, parallel to the 1989 fracture.
    Description: Published
    Description: 336-341
    Description: partially_open
    Keywords: GPS ; Ground deformation ; Modelling ; Volcano monitoring ; 04. Solid Earth::04.03. Geodesy::04.03.07. Satellite geodesy ; 04. Solid Earth::04.03. Geodesy::04.03.09. Instruments and techniques ; 04. Solid Earth::04.08. Volcanology::04.08.06. Volcano monitoring
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 6
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    A multi-disciplinary study of the 200203 Etna eruption: insights into a complex plumbing system (2005)
    Springer
    Details
    Publication Date: 2017-04-04
    Description: The 200203 Mt Etna flank eruption began on 26 October 2002 and finished on 28 January 2003, after three months of continuous explosive activity and discontinuous lava flow output. The eruption involved the opening of eruptive fissures on the NE and S flanks of the volcano, with lava flow output and fire fountaining until 5 November. After this date, the eruption continued exclusively on the S flank, with continuous explosive activity and lava flows active between 13 November and 28 January 2003. Multi-disciplinary data collected during the eruption (petrology, analyses of ash components, gas geochemistry, field surveys, thermal mapping and structural surveys) allowed us to analyse the dynamics of the eruption. The eruption was triggered either by (i) accumulation and eventual ascent of magma from depth or (ii) depressurisation of the edifice due to spreading of the eastern flank of the volcano. The extraordinary explosivity makes the 200203 eruption a unique event in the last 300 years, comparable only with La Montagnola 1763 and the 2001 Lower Vents eruptions. A notable feature of the eruption was also the simultaneous effusion of lavas with different composition and emplacement features. Magma erupted from the NE fissure represented the partially degassed magma fraction normally residing within the central conduits and the shallow plumbing system. The magma that erupted from the S fissure was the relatively undegassed, volatile-rich, buoyant fraction which drained the deep feeding system, bypassing the central conduits. This is typical of most Etnean eccentric eruptions. We believe that there is a high probability that Mount Etna has entered a new eruptive phase, with magma being supplied to a deep reservoir independent from the central conduit, that could periodically produce sufficient overpressure to propagate a dyke to the surface and generate further flank eruptions.
    Description: Published
    Description: 314-330
    Description: partially_open
    Keywords: Multi-disciplinary study ; Mount Etna ; 2002–03 eruption ; Eccentric eruptions ; Flank activity ; Etna feeding system ; Volcanic processes ; 04. Solid Earth::04.08. Volcanology::04.08.06. Volcano monitoring ; 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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  • 7
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    Chemical composition of precipitation at Mt. Vesuvius and Vulcano Island, Italy: volcanological and environmental implications (2010)
    Springer
    Details
    Publication Date: 2017-04-04
    Description: Natural precipitation and water samples from passive devices were collected at Mt. Vesuvius and Vulcano Island, Italy, during the period 2004–2006, in order to investigate its possible interactions with fumarolic gases. Evidence of chemical reactions between fumarolic fluids and rain samples before and after its deposition into the sampling devices was found at Vulcano Island. Very low pH values (down to 2.5) and significant amounts of chlorine and sulfate (up to 22 mEq/l) were measured at sampling points located close to the fumarolic field. In contrast, anthropogenic contributions and/or dissolution of aerosols (both maritime and continental) influence the chemistry of rainwaters at Mt. Vesuvius, which show inter-annual variations that are highly consistent with those recorded at the coastal site at Vulcano Island. Chemistry of waters directly exposed to fumarolic fluids may then give useful information about its temporal evolution, holding the signal of the ‘‘maximum’’ chemical event occurred in the meanwhile. In addition, the observation of the health status of vegetation colonizing the immediate surroundings of the fumarolic fields, due to its strong dependence on the interactions with these fluids, may work as a possible biomarker of volcanic activity
    Description: In press
    Description: 1.2. TTC - Sorveglianza geochimica delle aree vulcaniche attive
    Description: N/A or not JCR
    Description: reserved
    Keywords: Geochemistry ; Precipitation ; Fumarole ; 04. Solid Earth::04.08. Volcanology::04.08.06. Volcano monitoring
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 8
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    The role of the Pernicana Fault System in the spreading of Mt. Etna (Italy) during the 2002-2003 eruption (2005)
    Springer
    Details
    Publication Date: 2017-04-04
    Description: Flank instability and collapse are observed at many volcanoes. Among these, Mt. Etna is characterized by the spreading of its eastern and southern flanks. The eastern spreading area is bordered to the north by the EW-trending Pernicana Fault System (PFS). During the 20022003 Etna eruption, ground fracturing along the PFS migrated eastward from the NE Rift, to as far as the 18 km distant coastline. The deformation consisted of dextral en-echelon segments, with sinistral and normal kinematics. Both of these components of displacement were one order of magnitude larger (~1 m) in the western, previously known, portion of the PFS with respect to the newly surveyed (~9 km long) eastern section (~0.1 m). This eastern section is located along a pre-existing, but previously unknown, fault, where displaced man-made structures give overall slip rates (11.9 cm/year), only slightly lower than those calculated for the western portion (1.42.3 cm/year). After an initial rapid motion during the first days of the 20022003 eruption, movement of the western portion of the PFS decreased dramatically, while parts of the eastern portion continued to move. These data suggest a model of spreading of the eastern flank of Etna along the PFS, characterized by eruptions along the NE Rift, instantaneous, short-lived, meter-scale displacements along the western PFS and more long-lived centimeter-scale displacements along the eastern PFS. The surface deformation then migrated southwards, reactivating, one after the other, the NNWSSE-trending Timpe and Trecastagni faults, with displacements of ~0.1 and ~0.04 m, respectively. These structures, along with the PFS, mark the boundaries of two adjacent blocks, moving at different times and rates. The new extent of the PFS and previous activity over its full length indicate that the sliding eastern flank extends well below the Ionian Sea. The clustering of seismic activity above 4 km b.s.l. during the eruption suggests a deep décollement for the moving mass. The collected data thus suggests a significant movement (volume 〉1,100 km3) of the eastern flank of Etna, both on-shore and off-shore.
    Description: Published
    Description: 417-430
    Description: partially_open
    Keywords: Volcano spreading ; Fracturing ; Mt. Etna ; Pernicana Fault System ; NE Rift ; 04. Solid Earth::04.04. Geology::04.04.09. Structural geology ; 04. Solid Earth::04.08. Volcanology::04.08.06. Volcano monitoring ; 05. General::05.02. Data dissemination::05.02.03. Volcanic eruptions ; 04. Solid Earth::04.08. Volcanology::04.08.08. Volcanic risk
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
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  • 9
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    Ground deformation modeling of flank dynamics prior to the 2002 eruption of Mt. Etna (2007)
    Springer
    Details
    Publication Date: 2017-04-04
    Description: On 22 September 2002, 1 month before the beginning of the flank eruption on the NE Rift, an M-3.7 earthquake struck the northeastern part of Mt. Etna, on the westernmost part of the Pernicana fault. In order to investigate the ground deformation pattern associated with this event, a multi-disciplinary approach is presented here. Just after the earthquake, specific GPS surveys were carried out on two small sub-networks, aimed at monitoring the eastern part of the Pernicana fault, and some baselines belonging to the northeastern EDM monitoring network of Mt. Etna were measured. The leveling route on the northeastern flank of the volcano was also surveyed. Furthermore, an investigation using SAR interferometry was performed and also the continuous tilt data recorded at a high precision sensor close to the epicenter were analyzed to constrain the coseismic deformation. The results of the geodetic surveys show a ground deformation pattern that affects the entire northeastern flank of the volcano, clearly shaped by the Pernicana fault, but too strong and wide to be related only to an M-3.7 earthquake. Leveling and DInSAR data highlight a local strong subsidence, up to 7 cm, close to the Pernicana fault. Significant displacements, up to 2 cm, were also detected on the upper part of the NE Rift and in the summit craters area, while the displacements decrease at lower altitude, suggesting that the dislocation did not continue further eastward. Three-dimensional GPS data inversions have been attempted in order to model the ground deformation source and its relationship with the volcano plumbing system. The model has also been constrained by vertical displacements measured by the leveling survey and by the deformation map obtained by SAR interferometry.
    Description: Published
    Description: 757-768
    Description: 1.3. TTC - Sorveglianza geodetica delle aree vulcaniche attive
    Description: 3.6. Fisica del vulcanismo
    Description: JCR Journal
    Description: partially_open
    Keywords: Ground deformation ; Modeling ; Flank dynamics ; Volcano-tectonics ; 04. Solid Earth::04.03. Geodesy::04.03.01. Crustal deformations ; 04. Solid Earth::04.03. Geodesy::04.03.06. Measurements and monitoring ; 04. Solid Earth::04.08. Volcanology::04.08.06. Volcano monitoring
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  • 10
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    Chemical and isotopic compositions of thermal springs, fumaroles and bubbling gases at Tacaná Volcano (Mexico–Guatemala): implications for volcanic surveillance (2008)
    Springer
    Details
    Publication Date: 2017-04-04
    Description: This study presents baseline data for future geochemical monitoring of the active Tacaná volcano–hydrothermal system (Mexico–Guatemala). Seven groups of thermal springs, related to a NW/SE-oriented fault scarp cutting the summit area (4,100m a.s.l.), discharge at the northwest foot of the volcano (1,500–2,000m a.s.l.); another one on the southern ends of Tacaná (La Calera). The near-neutral (pH from 5.8 to 6.9) thermal (T from 25.7°C to 63.0°C) HCO3–SO4 waters are thought to have formed by the absorption of a H2S/SO2–CO2-enriched steam into a Cl-rich geothermal aquifer, afterwards mixed by Na/HCO3-enriched meteoric waters originating from the higher elevations of the volcano as stated by the isotopic composition (δD and δ18O) of meteoric and spring waters. Boiling temperature fumaroles (89°C at~3,600m a.s.l. NW of the summit), formed after the May 1986 phreatic explosion, emit isotopically light vapour (δD and δ18O as low as −128 and −19.9‰, respectively) resulting from steam separation from the summit aquifer. Fumarolic as well as bubbling gases at five springs are CO2-dominated. The δ13CCO2 for all gases show typical magmatic values of −3.6 ± 1.3‰ vs V-PDB. The large range in 3He/4He ratios for bubbling, dissolved and fumarolic gases [from 1.3 to 6.9 atmospheric 3He/4He ratio (RA)] is ascribed to a different degree of near-surface boiling processes inside a heterogeneous aquifer at the contact between the volcanic edifice and the crystalline basement (4He source). Tacaná volcano offers a unique opportunity to give insight into shallow hydrothermal and deep magmatic processes affecting the CO2/3He ratio of gases: bubbling springs with lower gas/water ratios show higher 3He/4He ratios and consequently lower CO2/3He ratios (e.g. Zarco spring). Typical Central American CO2/3He and 3He/4He ratios are found for the fumarolic Agua Caliente and Zarco gases (3.1 ± 1.6 × 1010 and 6.0 ± 0.9 RA, respectively). The L/S (5.9 ± 0.5)and (L + S)/M ratios (9.2 ± 0.7) for the same gases are almost identical to the ones calculated for gases in El Salvador, suggesting an enhanced slab contribution as far as the northern extreme of the Central American Volcanic Arc,Tacana
    Description: In press
    Description: 1.2. TTC - Sorveglianza geochimica delle aree vulcaniche attive
    Description: 2.4. TTC - Laboratori di geochimica dei fluidi
    Description: JCR Journal
    Description: reserved
    Keywords: Tacaná volcano ; Fluid geochemistry ; Volcano–hydrothermal system ; Bubbling gases ; Fumaroles ; Isotopes ; Volcanic surveillance ; 04. Solid Earth::04.04. Geology::04.04.12. Fluid Geochemistry ; 04. Solid Earth::04.08. Volcanology::04.08.01. Gases ; 04. Solid Earth::04.08. Volcanology::04.08.06. Volcano monitoring ; 05. General::05.02. Data dissemination::05.02.01. Geochemical data
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  • 11
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    Relationship between soil CO2 flux and volcanic tremor at Mt. Etna: Implications for magma dynamics (2009)
    Springer
    Details
    Publication Date: 2017-04-04
    Description: Large variations of the CO2 flux through the soil were observed between November 2002 and January 2006 at Mt. Etna volcano. In many cases, the CO2 flux was strongly influenced by changes in air temperature and atmospheric pressure. A new filtering method was then developed to remove the atmospheric influences on soil CO2 flux and, at the same time, to highlight the variations strictly related to volcanic activity. Successively, the CO2 corrected data were quantitatively compared with the spectral amplitude of the volcanic tremor by cross correlation function, cross-wavelet spectrum and wavelet coherence. These analyses suggested that the soil CO2 flux variations preceded those of volcanic tremor by about 50 days. Given that volcanic tremor is linked to the shallow (a few kilometer) magma dynamics and soil CO2 flux related to the deeper (*12 km b.s.l.) magma dynamics, the “delayed similarity” between the CO2 flux and the volcanic tremor amplitude was used to assess the average speed in the magma uprising into the crust, as about 170–260 m per day. Finally, the large amount of CO2 released before the onset of the 2004–2005 eruption indicated a deep ingression of new magma, which might have triggered such an eruption.
    Description: In press
    Description: N/A or not JCR
    Description: reserved
    Keywords: Mt. Etna ; Soil CO2 flux ; Volcanic tremor ; Cross-wavelet spectrum ; Wavelet coherence ; Cross correlation function ; 04. Solid Earth::04.08. Volcanology::04.08.06. Volcano monitoring ; 05. General::05.02. Data dissemination::05.02.01. Geochemical data ; 05. General::05.02. Data dissemination::05.02.02. Seismological data
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  • 12
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    The morphology and evolution of the Stromboli 2002–2003 lava flow field: an example of a basaltic flow field emplaced on a steep slope (2007)
    Springer
    Details
    Publication Date: 2017-04-04
    Description: The use of a hand-held thermal camera during the 2002–2003 Stromboli effusive eruption proved essential in tracking the development of flow field structures and in measuring related eruption parameters, such as the number of active vents and flow lengths. The steep underlying slope on which the flow field was emplaced resulted in a characteristic flow field morphology. This comprised a proximal shield, where flow stacking and inflation caused piling up of lava on the relatively flat ground of the vent zone, that fed a medial–distal lava flow field. This zone was characterized by the formation of lava tubes and tumuli forming a complex network of tumuli and flows linked by tubes. Most of the flow field was emplaced on extremely steep slopes and this had two effects. It caused flows to slide, as well as flow, and flow fronts to fail frequently, persistent flow front crumbling resulted in the production of an extensive debris field. Channel-fed flows were also characterized by development of excavated debris levees in this zone (Calvari et al. 2005). Collapse of lava flow fronts and inflation of the upper proximal lava shield made volume calculation very difficult. Comparison of the final field volume with that expecta by integrating the lava effusion rates through time suggests a loss of ~70% erupted lava by flow front crumbling and accumulation as debris flows below sea level. Derived relationships between effusion rate, flow length, and number of active vents showed systematic and correlated variations with time where spreading of volume between numerous flows caused an otherwise good correlation between effusion rate, flow length to break down. Observations collected during this eruption are useful in helping to understand lava flow processes on steep slopes, as well as in interpreting old lava–debris sequences found in other steep-sided volcanoes subject to effusive activity.
    Description: Published
    Description: JCR Journal
    Description: reserved
    Keywords: Lava flow field ; Morphology ; Tumuli ; Lava tubes ; Effusion rate ; Rheology ; Stromboli volcano ; 04. Solid Earth::04.08. Volcanology::04.08.06. Volcano monitoring ; 04. Solid Earth::04.08. Volcanology::04.08.07. Instruments and techniques ; 04. Solid Earth::04.08. Volcanology::04.08.08. Volcanic risk
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  • 13
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    Major-ion bulk deposition around an active volcano (Mt. Etna, Italy) (2007)
    Springer
    Details
    Publication Date: 2017-04-04
    Description: Bulk atmospheric deposition of major cations (Na, K, Ca, Mg) and anions (Cl, F, SO4) were measured at 15 sites around an active volcano, Mount Etna, from 2001 to 2003. Their composition indicates several natural sources, among which deposition of plume-derived volcanogenic gas compounds is prevalent for F, Cl and S. Plume-derived acidic compounds are also responsible for the prevailing acidic composition of the samples collected on the summit of the volcano (pH in the 2.45–5.57 range). Cation species have complex origin, including deposition of plume volcanogenic ash and aerosols and soil-dust wind re-suspension of either volcanic or carbonate sedimentary rocks. Variation of the deposition rates during the March 2001– March 2003 period, coupled with previous measurements from 1997 to 2000 (Appl Geochem 16:985–1000, 2001), were compared with the variation of SO2 flux, volcanic activity and rainfall. The deposition rate was mainly controlled by rainfall. Commonly, about 0.1–0.9% of HF, HCl and SO2 emitted by the summit crater’s plume were deposited around the volcano. We estimate that ∼2 Gg of volcanogenic sulphur were deposited over the Etnean area during the 2002–2003 flank eruption, at an average rate of ∼24 Mg day−1 which is two orders of magnitude higher than that typical of quiescent degassing phases.
    Description: Published
    Description: 255-265
    Description: JCR Journal
    Description: open
    Keywords: Volcanic degassing ; Etna volcano ; Impact of volcanic eruptions ; S deposition rates ; Halogen deposition rates ; Bulk deposition chemistry ; Environmental volcanology ; 04. Solid Earth::04.08. Volcanology::04.08.06. Volcano monitoring
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 14
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    Strombolian explosive styles and source conditions: insights from thermal (FLIR) video (2007)
    Springer
    Details
    Publication Date: 2017-04-04
    Description: Forward Looking Infrared Radiometer (FLIR) cameras offer a unique view of explosive volcanism by providing an image of calibrated temperatures. In this study, 344 eruptive events at Stromboli volcano, Italy, were imaged in 2001–2004 with a FLIR camera operating at up to 30 Hz. The FLIR was effective at revealing both ash plumes and coarse ballistic scoria, and a wide range of eruption styles was recorded. Eruptions at Stromboli can generally be classified into two groups: Type 1 eruptions, which are dominated by coarse ballistic particles, and Type 2 eruptions, which consist of an optically-thick, ash-rich plume, with (Type 2a) or without (Type 2b) large numbers of ballistic particles. Furthermore, Type 2a plumes exhibited gas thrust velocities (〉15 m s−1) while Type 2b plumes were limited to buoyant velocities (〈15 m s−1) above the crater rim. A given vent would normally maintain a particular gross eruption style (Type 1 vs. 2) for days to weeks, indicating stability of the uppermost conduit on these timescales. Velocities at the crater rim had a range of 3–101 m s−1, with an overall mean value of 24 m s−1. Mean crater rim velocities by eruption style were: Type 1= 34 m s−1, Type 2a=31 m s−1, Type 2b=7 m s−1. Eruption durations had a range of 6–41 s, with a mean of 15 s, similar among eruption styles. The ash in Type 2 eruptions originates from either backfilled material (crater wall slumping or ejecta rollback) or rheological changes in the uppermost magma column. Type 2a and 2b behaviors are shown to be a function of the overpressure of the bursting slug. In general, our imaging data support a broadening of the current paradigm for strombolian behavior, incorporating an uppermost conduit that can be more variable than is commonly considered.
    Description: NSF grant no. EAR-0207734, NERC grant no. NER/B/S/2001/00707, the USGS Volcano Hazards Program and the Geophysical Institute at the University of Alaska Fairbanks
    Description: Published
    Description: 769-784
    Description: 1.5. TTC - Sorveglianza dell'attività eruttiva dei vulcani
    Description: JCR Journal
    Description: reserved
    Keywords: Stromboli volcano ; volcano monitoring ; thermal imaging ; eruption dynamics ; 04. Solid Earth::04.08. Volcanology::04.08.06. Volcano monitoring
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  • 15
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    Geochemical evidence of the renewal of volcanic activity inferred from CO2 soil and SO2 plume fluxes: the 2007 Stromboli eruption (Italy) (2011)
    Springer
    Details
    Publication Date: 2017-04-04
    Description: On 27 February 2007, a new eruption occurred on Stromboli which lasted until 2 April. It was characterized by effusive activity on the Sciara del Fuoco and by a paroxysmal event (15 March). This crisis represented an opportunity for us to refine the model that had been developed previously (2002–2003 eruption) and to improve our understanding of the relationship between the magmatic dynamics of the volcano and the geochemical variations in the fluids. In particular, the evaluation of the dynamic equilibrium between the volatiles (CO2 and SO2) released from the magma and the corresponding fluids discharged from the summit area allowed us to evaluate the level of criticality of the volcanic activity. One of the major accomplishments of this study is a 4-year database of summit soil CO2 flux on the basis of which we define the thresholds (low–medium–high) for this parameter that are empirically based on the natural volcanological evolution of Stromboli. The SO2 fluxes of the degassing plume and the CO2 fluxes emitted from the soil at Pizzo Sopra la Fossa are also presented. It is noteworthy that geochemical signals of volcanic unrest have been clearly identified before, during and after the effusive activity. These signals were found almost simultaneously in the degassing plume (SO2 flux) and in soil degassing (CO2 flux) at the summit, although the two degassing processes are shown to be clearly different. The interpretation of the results will be useful for future volcanic surveillance at Stromboli.
    Description: Published
    Description: 443-456
    Description: 1.2. TTC - Sorveglianza geochimica delle aree vulcaniche attive
    Description: 2.4. TTC - Laboratori di geochimica dei fluidi
    Description: JCR Journal
    Description: reserved
    Keywords: Stromboli volcano ; CO2 soil flux ; Geochemical monitoring ; 2007 eruption ; 04. Solid Earth::04.08. Volcanology::04.08.06. Volcano monitoring ; 04. Solid Earth::04.08. Volcanology::04.08.07. Instruments and techniques ; 05. General::05.02. Data dissemination::05.02.01. Geochemical data ; 05. General::05.02. Data dissemination::05.02.03. Volcanic eruptions
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  • 16
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    Towards an Automatic Monitoring System of Infrasonic Events at Mt. Etna: Strategies for Source Location and Modeling (2010)
    Springer
    Details
    Publication Date: 2017-04-04
    Description: Active volcanoes characterized by open conduit conditions generate sonic and infrasonic signals, whose investigation provides useful information for both monitoring purposes and studying the dynamics of explosive processes. In this work, we discuss the automatic procedures implemented for a real-time application to the data acquired by a permanent network of five infrasound stations running at Mt. Etna volcano. The infrasound signals at Mt. Etna consist in amplitude transients, called infrasound events. The adopted procedure uses a multi-algorithm approach for event detection, counting, characterization and location. It is designed for an efficient and accurate processing of infrasound records provided by single-site and array stations. Moreover, the source mechanism of these events can be investigated off-line or in near real-time by using three different models: (1) Strombolian bubble; (2) resonating conduit and (3) Helmholtz resonator. The infrasound waveforms allow us to choose the most suitable model, to get quantitative information about the source and to follow the time evolution of the source parameters.
    Description: Published
    Description: 1215–1231
    Description: 1.4. TTC - Sorveglianza sismologica delle aree vulcaniche attive
    Description: JCR Journal
    Description: reserved
    Keywords: Infrasound ; monitoring system ; Mt. Etna volcano ; 04. Solid Earth::04.06. Seismology::04.06.08. Volcano seismology ; 04. Solid Earth::04.08. Volcanology::04.08.06. Volcano monitoring ; 04. Solid Earth::04.08. Volcanology::04.08.07. Instruments and techniques
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  • 17
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    New clues on the contribution of Earth’s volcanism to the global mercury cycle (2011)
    Springer
    Details
    Publication Date: 2017-04-04
    Description: Active volcanoes are thought to be important contributors to the atmospheric mercury (Hg) budget, and this chemical element is one of the most harmful atmospheric pollutants, owing to its high toxicity and long residence time in ecosystems. There is, however, considerable uncertainty over the magnitude of the global volcanic Hg flux, since the existing data on volcanogenic Hg emissions are sparse and often ambiguous. In an attempt to extend the currently limited dataset on volcanogenic Hg emissions, we summarize the results of Hg flux measurements at seven active open-conduit volcanoes; Stromboli, Asama, Miyakejima, Montserrat, Ambrym, Yasur, and Nyiragongo.. Data from the domebuilding Soufriere Hills volcano are also reported. Using our determined mercury to SO2 mass ratios in tandem with the simultaneously-determined SO2 emission rates, we estimate that the 7 volcanoes have Hg emission rates ranging from 0.2 to 18 t yr-1 (corresponding to a total Hg flux of ~41 t·yr-1). Based on our dataset and previous work, we propose that a Hg/SO2 plume ratio ~10-5 is bestrepresentative of gas emissions from quiescent degassing volcanoes. Using this ratio, we infer a global volcanic Hg flux from persistent degassing of ~95 t·yr-1
    Description: Published
    Description: 497-510
    Description: 1.2. TTC - Sorveglianza geochimica delle aree vulcaniche attive
    Description: 2.4. TTC - Laboratori di geochimica dei fluidi
    Description: JCR Journal
    Description: restricted
    Keywords: Volcanogenic mercury ; Mercury ; Volcanic plume ; Mercury flux ; Mercury inventories ; Atmospheric mercury ; 01. Atmosphere::01.01. Atmosphere::01.01.07. Volcanic effects ; 04. Solid Earth::04.02. Exploration geophysics::04.02.01. Geochemical exploration ; 04. Solid Earth::04.04. Geology::04.04.12. Fluid Geochemistry ; 04. Solid Earth::04.08. Volcanology::04.08.01. Gases ; 04. Solid Earth::04.08. Volcanology::04.08.06. Volcano monitoring
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  • 18
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    CO2 and He degassing at El Chichón volcano, Chiapas, Mexico: gas flux, origin and relationship with local and regional tectonics (2011)
    Springer
    Details
    Publication Date: 2017-04-04
    Description: During 2007–2008, three CO2 flux surveys were performed on El Chichón volcanic lake, Chiapas, Mexico, with an additional survey in April 2008 covering the entire crater floor (including the lake). The mean CO2 flux calculated by sequential Gaussian simulation from the lake was 1,190 (March 2007), 730 (December 2007) and 1,134 g m−2 day−1 (April 2008) with total emission rates of 164±9.5 (March 2007), 59±2.5 (December 2007) and 109±6.6 t day−1 (April 2008). The mean CO2 flux estimated from the entire crater floor area was 1,102 g m−2 day−1 for April 2008 with a total emission rate of 144±5.9 t day−1. Significant change in CO2 flux was not detected during the period of survey, and the mapping of the CO2 flux highlighted lineaments reflecting the main local and regional tectonic patterns. The 3He/4He ratio (as high as 8.1 RA) for gases in the El Chichón crater is generally higher than those observed at the neighbouring Transmexican Volcanic Belt and the Central American Volcanic Arc. The CO2/3He ratios for the high 3He/4He gases tend to have the MORB-like values (1.41×109), and the CO2/3He ratios for the lower 3He/4He gases fall within the range for the arc-type gases. The high 3He/4He ratios, the MORB-like CO2/3He ratios for the high 3He/4He gases and high proportion of MORB-CO2 (M=25 ±15%) at El Chichón indicate a greater depth for the generation of magma when compared to typical arc volcanoes.
    Description: Published
    Description: 423-441
    Description: 2.4. TTC - Laboratori di geochimica dei fluidi
    Description: JCR Journal
    Description: reserved
    Keywords: El Chichon ; CO2 soil flux ; Crater Lake ; Gas geochemistry ; He-C isotopes ; Fumarolic and bubbling gases ; Tectonics ; 04. Solid Earth::04.04. Geology::04.04.12. Fluid Geochemistry ; 04. Solid Earth::04.05. Geomagnetism::04.05.08. Instruments and techniques ; 04. Solid Earth::04.06. Seismology::04.06.06. Surveys, measurements, and monitoring ; 04. Solid Earth::04.08. Volcanology::04.08.01. Gases ; 04. Solid Earth::04.08. Volcanology::04.08.06. Volcano monitoring ; 05. General::05.02. Data dissemination::05.02.01. Geochemical data
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  • 19
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    Analysis of Lava Flow Effusion Rate Using High Spatial Resolution Infrared Data (2014)
    Springer
    Details
    Publication Date: 2017-04-04
    Description: Remote sensing thermal data of active lava flows allow for the evaluation of instantaneous effusion rates. This is made possible by simple formulae relating the lava effusion rate to the power energy radiated per unit time from the surface to the flow. Such formulae are based on a specific flow model and, consequently, their validity is subject to the model assumptions. The most questionable assumption is probably the constancy of the surface temperature. Herein, we use high spatial resolution infrared data to demonstrate the existence of an underlying relationship between the surface temperature and the lava flow thickness, using the 2001 Mt. Etna flow as a case study. According to this relationship, observed changes in surface temperature does not represent a weakness of the model but is the expected consequence of actual variations in the topographic down flow profile.
    Description: Published
    Description: 391-408
    Description: 3V. Dinamiche e scenari eruttivi
    Description: restricted
    Keywords: Remote sensing, effusion rate, heat flux, Etna, MIVIS ; 04. Solid Earth::04.08. Volcanology::04.08.06. Volcano monitoring
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: book chapter
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  • 20
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    Long-time variation of soil CO2 fluxes at the summit crater of Vulcano (Italy) (2014)
    Springer
    Details
    Publication Date: 2017-04-04
    Description: Here, we report the first continuous data of geochemical parameters acquired directly from the active summit crater of Vulcano. This approach provides a means to better investigate deep geochemical processes associated with the degassing system of Vulcano Island. In particular, we report on soil CO2 fluxes from the upper part of Vulcano, a closed-conduit volcano, from September 2007 to October 2010. Large variations in the soil CO2 and plume SO2 fluxes (order of magnitude), coinciding with other discontinuous geochemical parameters (CO2 concentrations in fumarole gas) and physical parameters (increase of shallow seismic activity and fumarole temperatures) have been recorded. The results from this work suggest new prospects for strengthening geochemical monitoring of volcanic activity and for improving the constraints in the construction of a “geochemical model”, this being a necessary condition to better understand the functioning of volcanic systems.
    Description: Published
    Description: 1859-1863
    Description: 2V. Dinamiche di unrest e scenari pre-eruttivi
    Description: 4V. Vulcani e ambiente
    Description: 5V. Sorveglianza vulcanica ed emergenze
    Description: 1R. Reti di monitoraggio e Osservazioni
    Description: JCR Journal
    Description: restricted
    Keywords: Vulcano Island ; Geochemical monitoring ; CO2 flux ; CO2 fumaroles ; SO2 flux ; 01. Atmosphere::01.01. Atmosphere::01.01.07. Volcanic effects ; 04. Solid Earth::04.08. Volcanology::04.08.01. Gases ; 04. Solid Earth::04.08. Volcanology::04.08.06. Volcano monitoring ; 04. Solid Earth::04.08. Volcanology::04.08.08. Volcanic risk ; 05. General::05.02. Data dissemination::05.02.01. Geochemical data
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  • 21
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    Geochemical evidence of the renewal of volcanic activity 5 inferred from CO2 soil and SO2 plume fluxes: the 2007 6 Stromboli eruption (Italy) (2011)
    Springer
    Details
    Publication Date: 2020-02-24
    Description: On 27 February 2007, a new eruption occurred on Stromboli which lasted until 2 April. It was characterized by effusive activity on the Sciara del Fuoco and by a paroxysmal event (15 March). This crisis represented an opportunity for us to refine the model that had been developed previously (2002-2003 eruption) and to improve our understanding of the relationship between the magmatic dynamics of the volcano and the geochemical variations in the fluids. In particular, the evaluation of the dynamic equilibrium between the volatiles (CO2 and SO2) released from the magma and the corresponding fluids discharged from the summit area allowed us to evaluate the level of criticality of the volcanic activity. One of the major accomplishments of this study is a four-year database of summit soil CO2 flux on the basis of which we define the thresholds (Low-Medium-High) for this parameter that are empirically based on the natural volcanological evolution of Stromboli. The SO2 fluxes of the degassing plume and the CO2 fluxes emitted from the soil at Pizzo Sopra la Fossa are also presented. Noteworthy geochemical signals of volcanic unrest have been clearly identified before, during, and after the effusive activity. These signals were found almost simultaneously in the degassing plume (SO2 flux) and in soil degassing (CO2 flux) at the summit, although the two degassing processes are shown to be clearly different. The interpretation of the results will be useful for future volcanic surveillance at Stromboli.
    Description: In press
    Description: 2.4. TTC - Laboratori di geochimica dei fluidi
    Description: JCR Journal
    Description: reserved
    Keywords: Stromboli Volcano ; CO2 soil flux ; Geochemical monitoring ; 2007 eruption ; 04. Solid Earth::04.04. Geology::04.04.12. Fluid Geochemistry ; 04. Solid Earth::04.06. Seismology::04.06.10. Instruments and techniques ; 04. Solid Earth::04.08. Volcanology::04.08.01. Gases ; 04. Solid Earth::04.08. Volcanology::04.08.06. Volcano monitoring
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  • 22
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    Slug Flow: Modeling in a Conduit and Associated Elastic Radiation (2012)
    Springer
    Details
    Publication Date: 2017-04-03
    Description: Among the eruptive styles, the Strombolian activity is one of the more easy to study because of its repetitive behavior. For this reason large amount of data can be comfortably collected. Strombolian volcanoes are like natural laborato- ries repeating the same experiment (individual explosions) many times each day. The development of quantitative models of eruptive dynamics is driven by the comparison of experimental ob- servations and synthetic data obtained through mathemat- ical, numerical or analogue modeling. Since Strombolian activity offers a profuse amount of interesting seismic signals, during the last decades there has been growing attention on seismological techniques aimed at retrieving the conduit geometry and the eruption dynamics from the seismological recordings. One of these techniques, the source function inversion, is able to re- trieve a summary of the forces acting on the volcanic con- duit during the VLP event generation [5]. The comparison of observed source functions with synthetic ones, obtained through numerical modeling, allow us to put constraints on the proposed models. Quantitative models, able to fit seismological observa- tions, are a powerful tool for interpreting seismic record- ings and therefor the seismological monitoring of active volcanoes.
    Description: Published
    Description: 1.4. TTC - Sorveglianza sismologica delle aree vulcaniche attive
    Description: restricted
    Keywords: Strombolian activity ; Slug flow ; 04. Solid Earth::04.06. Seismology::04.06.08. Volcano seismology ; 04. Solid Earth::04.08. Volcanology::04.08.06. Volcano monitoring ; 05. General::05.01. Computational geophysics::05.01.99. General or miscellaneous
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: book chapter
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  • 23
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    Multiparametric Approach in Investigating Volcano-Hydrothermal Systems: the Case Study of Vulcano (Aeolian Islands, Italy) (2012)
    Springer
    Details
    Publication Date: 2017-04-04
    Description: Seismic activity, ground deformation, and soil and fumarole temperatures acquired during 2004–2007 at Vulcano (Aeolian Islands) are analysed and the time relations among the different time series are discussed. Changes in temperature of fumarolic gases took place during four ‘‘anomalous’’ periods (November 2004–March 2005; October 2005–February 2006; August–October 2006; July–December 2007) at the same time as an increasing number of volcano-seismic events. In particular, the temperatures at high temperature vents and at steam heated soil ranged in time from 180 to 440 C and from 20 to 90 C, respectively. The maximum daily number of volcano-seismic events was 57, reached during the second anomalous period. This seismicity, characterised by focal depth generally lower than 1 km below sea level (b.s.l.) and composed of different kinds of events associated to both resonance and shear failure processes, is related to the shallow dynamics of the hydrothermal system. During the analysed period, very few volcano-tectonic earthquakes took place and tilt recordings showed no sharp or important changes. In light of such observations, the increases in both temperature and volcano-seismic events number were associated to increases in the release of gas from a deep and stable magma body, without magma intrusions within the shallow hydrothermal system. Indeed, a greater release of gas from depth leads to increased fluid circulation, that can promote increases in volcano-seismic events number by both fracturing processes and resonance and vibration in cracks and conduits. The different trends observed in the measured geochemical and geophysical series during the anomalous periods can be due to either time changes in the medium permeability or a changing speed of gas release from a deep magma body. Finally, all the observed variations, together with the changing temporal distribution of the different seismic event kinds, suggest that the hydrothermal system at Vulcano can be considered unsteady and dynamic.
    Description: Published
    Description: 167–182
    Description: 1.5. TTC - Sorveglianza dell'attività eruttiva dei vulcani
    Description: JCR Journal
    Description: reserved
    Keywords: Volcano seismolog ; soil and fumarole temperatures ; tilt data ; hydrothermal system ; Vulcano Island ; volcanic unrest ; 04. Solid Earth::04.06. Seismology::04.06.08. Volcano seismology ; 04. Solid Earth::04.08. Volcanology::04.08.01. Gases ; 04. Solid Earth::04.08. Volcanology::04.08.06. Volcano monitoring
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  • 24
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    Degassing, crystallization and eruption dynamics at Stromboli: trace element and lithium isotopic evidence from 2003 ashes (2011)
    Springer
    Details
    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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  • 25
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    First 13C/12C isotopic characterisation of volcanic plume CO2 (2011)
    Springer
    Details
    Publication Date: 2017-04-04
    Description: We describe analytical details and uncertainty evaluation of a simple technique for the measurement of the carbon isotopic composition of CO2 in volcanic plumes. Data collected at Solfatara and Vulcano, where plumes are fed by fumaroles which are accessible for direct sampling, were first used to validate the technique. For both volcanoes, the plume-derived carbon isotopic compositions are in good agreement with the fumarolic compositions, thus providing confidence on the method, and allowing its application at volcanoes where the volcanic component is inaccessible to direct sampling. As a notable example, we applied the same method to Mount Etna where we derived a δ13C of volcanic CO2 between −0.9 ± 0.27‰ and −1.41 ± 0.27‰ (Bocca Nuova and Voragine craters). The comparison of our measurements to data reported in previous work highlights a temporal trend of systematic increase of δ13C values of Etna CO2 from ~ −4‰, in the 1970’s and the 1980’s, to ~ −1‰ at the present time (2009). This shift toward more positive δ13C values matches a concurrent change in magma composition and an increase in the eruption frequency and energy. We discuss such variations in terms of two possible processes: magma carbonate assimilation and carbon isotopic fractionation due to magma degassing along the Etna plumbing system. Finally, our results highlight potential of systematic measurements of the carbon isotopic composition of the CO2 emitted by volcanic plumes for a better understanding of volcanic processes and for improved surveillance of volcanic activity.
    Description: In press
    Description: 1.2. TTC - Sorveglianza geochimica delle aree vulcaniche attive
    Description: 2.4. TTC - Laboratori di geochimica dei fluidi
    Description: JCR Journal
    Description: reserved
    Keywords: Volcanic plume ; Carbon isotope ; Etna ; Magmatic degassing ; 04. Solid Earth::04.08. Volcanology::04.08.01. Gases ; 04. Solid Earth::04.08. Volcanology::04.08.06. Volcano monitoring ; 04. Solid Earth::04.08. Volcanology::04.08.07. Instruments and techniques
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  • 26
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    Relationship between soil CO2 flux and volcanic tremor at Mt. Etna: Implications for magma dynamics (2011)
    Springer
    Details
    Publication Date: 2017-04-04
    Description: Large variations of the CO2 flux through the soil were observed between November 2002 and January 2006 at Mt. Etna volcano. In many cases, the CO2 flux was strongly influenced by changes in air temperature and atmospheric pressure. A new filtering method was then developed to remove the atmospheric influences on soil CO2 flux and, at the same time, to highlight the variations strictly related to volcanic activity. Successively, the CO2 corrected data were quantitatively compared with the spectral amplitude of the volcanic tremor by cross correlation function, cross-wavelet spectrum and wavelet coherence. These analyses suggested that the soil CO2 flux variations preceded those of volcanic tremor by about 50 days. Given that volcanic tremor is linked to the shallow (a few kilometer) magma dynamics and soil CO2 flux related to the deeper (*12 km b.s.l.) magma dynamics, the ‘‘delayed similarity’’ between the CO2 flux and the volcanic tremor amplitude was used to assess the average speed in the magma uprising into the crust, as about 170–260 mper day. Finally, the large amount of CO2 released before the onset of the 2004–2005 eruption indicated a deep ingression of new magma, which might have triggered such an eruption.
    Description: Published
    Description: 477–489
    Description: 3.6. Fisica del vulcanismo
    Description: JCR Journal
    Description: reserved
    Keywords: Mt. Etna volcano ; volcanic tremor ; soil CO2 ; 04. Solid Earth::04.08. Volcanology::04.08.06. Volcano monitoring
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  • 27
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    Changes of the susceptibility to lava flow invasion induced by morphological modifications of an active volcano: the case of Mount Etna, Italy (2011)
    Springer
    Details
    Publication Date: 2017-04-04
    Description: Changes of the susceptibility to lava flow invasion at Mount Etna are quantified by using lava flow simulations on four Digital Elevation Models documenting the morphostructural modifications of the volcano in the time interval 1986–2007. The probabilistic code DOWNFLOW is used to derive the areas invaded by several thousands of lava flows obtaining, for each DEM, maps of the susceptibility to lava flow invasion and of the lava flow hazard. These maps show, for the first time, the evolution of these surficial properties with time, and render a quantitative image of the effects of topographic changes on the preferential lava flow drainage paths. The results illustrate how the emplacement of new lava flows and the growth of scoria cones affect the probability of inundation by lava flows. We conclude that the persistent activity of this volcano requires a frequent updating of the topography for a reliable lava flow hazard assessment.
    Description: Published
    Description: 537-546
    Description: 3.5. Geologia e storia dei vulcani ed evoluzione dei magmi
    Description: 4.3. TTC - Scenari di pericolosità vulcanica
    Description: JCR Journal
    Description: reserved
    Keywords: Lava flow simulation ; Digital Elevation Model ; Lidar ; Time series ; Lava flow hazard maps ; 04. Solid Earth::04.08. Volcanology::04.08.06. Volcano monitoring ; 04. Solid Earth::04.08. Volcanology::04.08.08. Volcanic risk ; 05. General::05.08. Risk::05.08.99. General or miscellaneous
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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    Unknown
    Revisiting carbon flux through the ocean's twilight zone (2010)
    American Association for the Advancement of Science
    Details
    Publication Date: 2017-01-04
    Description: Citation only. Published in Science 316: 567-570, doi: 10.1126/science.1137959
    Description: Funding was obtained primarily through the NSF, Ocean Sciences Programs in Chemical and Biological Oceanography, with additional support from the U.S. Department of Energy, Office of Science, Biological and Environmental Research Program, and other national programs, including the Australian Cooperative Research Centre program and Australian Antarctic Division.
    Keywords: Carbon flux ; Carbon sequestration ; Biological pump
    Repository Name: Woods Hole Open Access Server
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    Electronic Resource
    Human Interindividual Variability in Parameters Related to Health Risks (1999)
    Springer
    Risk analysis 19 (1999), S. 711-726 
    Details
    ISSN: 1539-6924
    Keywords: variability ; exposure ; susceptibility ; risk assessment ; pharmacokinetics ; pharmacodynamics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Energy, Environment Protection, Nuclear Power Engineering
    Notes: Abstract This paper reviews existing data on the variability in parameters relevant for health risk analyses. We cover both exposure-related parameters and parameters related to individual susceptibility to toxicity. The toxicity/susceptibility data base under construction is part of a longer term research effort to lay the groundwork for quantitative distributional analyses of non-cancer toxic risks. These data are broken down into a variety of parameter types that encompass different portions of the pathway from external exposure to the production of biological responses. The discrete steps in this pathway, as we now conceive them, are: •Contact Rate (Breathing rates per body weight; fish consumption per body weight) •Uptake or Absorption as a Fraction of Intake or Contact Rate •General Systemic Availability Net of First Pass Elimination and Dilution via Distribution Volume (e.g., initial blood concentration per mg/kg of uptake) •Systemic Elimination (half life or clearance) •Active Site Concentration per Systemic Blood or Plasma Concentration •Physiological Parameter Change per Active Site Concentration (expressed as the dose required to make a given percentage change in different people, or the dose required to achieve some proportion of an individual's maximum response to the drug or toxicant) •Functional Reserve Capacity–Change in Baseline Physiological Parameter Needed to Produce a Biological Response or Pass a Criterion of Abnormal Function Comparison of the amounts of variability observed for the different parameter types suggests that appreciable variability is associated with the final step in the process–differences among people in “functional reserve capacity.” This has the implication that relevant information for estimating effective toxic susceptibility distributions may be gleaned by direct studies of the population distributions of key physiological parameters in people that are not exposed to the environmental and occupational toxicants that are thought to perturb those parameters. This is illustrated with some recent observations of the population distributions of Low Density Lipoprotein Cholesterol from the second and third National Health and Nutrition Examination Surveys.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1007045922532
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    Evaluation of the Uncertainty in an Oral Reference Dose for Methylmercury Due to Interindividual Variability in Pharmacokinetics (1999)
    Springer
    Risk analysis 19 (1999), S. 547-558 
    Details
    ISSN: 1539-6924
    Keywords: MeHg ; pharmacokinetics ; PBPK model ; variability ; risk assessment
    Source: Springer Online Journal Archives 1860-2000
    Topics: Energy, Environment Protection, Nuclear Power Engineering
    Notes: Abstract An analysis of the uncertainty in guidelines for the ingestion of methylmercury (MeHg) due to human pharmacokinetic variability was conducted using a physiologically based pharmacokinetic (PBPK) model that describes MeHg kinetics in the pregnant human and fetus. Two alternative derivations of an ingestion guideline for MeHg were considered: the U.S. Environmental Protection Agency reference dose (RfD) of 0.1 μg/kg/day derived from studies of an Iraqi grain poisoning episode, and the Agency for Toxic Substances and Disease Registry chronic oral minimal risk level (MRL) of 0.5 μg/kg/day based on studies of a fish-eating population in the Seychelles Islands. Calculation of an ingestion guideline for MeHg from either of these epidemiological studies requires calculation of a dose conversion factor (DCF) relating a hair mercury concentration to a chronic MeHg ingestion rate. To evaluate the uncertainty in this DCF across the population of U.S. women of child-bearing age, Monte Carlo analyses were performed in which distributions for each of the parameters in the PBPK model were randomly sampled 1000 times. The 1st and 5th percentiles of the resulting distribution of DCFs were a factor of 1.8 and 1.5 below the median, respectively. This estimate of variability is consistent with, but somewhat less than, previous analyses performed with empirical, one-compartment pharmacokinetic models. The use of a consistent factor in both guidelines of 1.5 for pharmacokinetic variability in the DCF, and keeping all other aspects of the derivations unchanged, would result in an RfD of 0.2 μg/kg/day and an MRL of 0.3 μg/kg/day.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1007017116171
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    Das Rückstandsverhalten von Chloramphenicol nach intramuskulärer Applikation beim Schwein (1985)
    Springer
    European journal of nutrition 24 (1985), S. 113-119 
    Details
    ISSN: 1436-6215
    Keywords: Chloramphenicol ; pharmacokinetics ; residue ; pig
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition , Medicine
    Description / Table of Contents: Summary Residues of Chloramphenicol (CAP) were examined in 24 pigs after intramuscular injection of 30 mg CAP/kg body weight. Two pigs were slaughtered after 3, 6, 12,18, 24, 36 hours, 2, 3, 6, 10, 21 and 30 days, respectively. CAP-concentrations were determined in muscle, blood, urine, liver, kidney, bile, and fat. Methods used were gas-liquid chromatography and radioimmunoassay. Detection limits reached were 1−5 ppb. The concentration-time curves obtained reflected a long elimination phase and allowed only calculation of this half-life. Elimination half-life was estimated to be for muscle, blood and urine 160–170 hours, for kidney 310 and for bile 250 hours. Significant correlations were found to exist between CAP-concentrations in plasma and muscle. It appears that blood would be a good body fluid for monitoring CAP-residues in tissue.
    Notes: Zusammenfassung Zur Untersuchung des Rückstandsverhaltens von Chloramphenicol (CAP) wurden 24 Mastschweine, 24–28 Wochen alt, intramuskulär mit 30 mg CAP/kg Körpergewicht behandelt und je 2 Tiere nach 3, 6, 12, 18, 24, 36 Stunden, 2, 3, 6, 10, 21 und 30 Tagen geschlachtet. Die CAP-Gehalte in Muskulatur, Blut, Urin, Leber, Niere, Galle und Fett wurden gaschromatographisch und radioimmunologisch bestimmt. Die Nachweisgrenze beider Methoden liegt in Abhängigkeit von der Matrix zwischen 1 und 5 ppb. Die erhaltenen Kinetiken weisen eine terminale Elimination auf, deren Halbwertszeiten für Muskulatur, Blut und Urin ca. 160–170 Stunden, für Niere 310 Stunden und für Galle 250 Stunden betragen. Die CAP-Konzentration in Muskulatur und Blut weisen eine signifikante, lineare Korrelation auf. Blutuntersuchungen könnten deshalb als Screening-Methode bei umfangreichen Rückstandskontrollen eingesetzt werden.
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    URL: http://dx.doi.org/10.1007/BF02020458
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    Enzymatic and pharmacokinetic studies on the metabolism of branched chain α-keto acids in the rat (1983)
    Springer
    European journal of nutrition 22 (1983), S. 14-26 
    Details
    ISSN: 1436-6215
    Keywords: branched chain α-keto acids ; 4-methyl-2-oxopentanoate, 3-methyl-2-oxopentanoate ; 3-methyl-2-oxobutyrate ; dehydrogenation ; transamination ; pharmacokinetics ; absorption
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition , Medicine
    Description / Table of Contents: Zusammenfassung Michaelis-Konstanten und Aktivitäten von Dehydrogenasen und Transaminasen der drei verzweigten α-Ketosäuren Keto-Valin, Keto-Leucin und Keto-Isoleucin in Leber, Niere, Skeletmuskel und Gehirn von Ratten werden mitgeteilt. Nach oraler Zufuhr passieren nur 11–22% der Ketosäuren unverändert die Leber. Aus pharmakokinetischen und Resorptions-Untersuchungen erhaltene Blutspiegel an Ketosäuren werden zu den Michaelis-Konstanten in Beziehung gesetzt. Bei den geringen Konzentrationen an Ketosäuren nach oraler Zufuhr kann angenommen werden, daß die oxidativen Prozesse in den nichthepatischen Geweben über die Transaminierung überwiegen. Daten über die Wachstumseffizienz von verzweigtkettigen α-Ketosäuren im Vergleich zu den entsprechenden Aminosäuren stimmen mit dieser Vorstellung überein. Bei intravenöser Verabreichung müßten die Voraussetzungen für Transaminierung besser sein als nach oraler Zufuhr. Auf der Basis von Daten aus der Literatur werden die Übertragbarkeit unserer Befunde auf den Menschen und die verschiedenen Faktoren, welche die Effizienz der verzweigten α-Ketosäuren durch Einwirkung auf ihren Stoffwechsel beeinflussen können, diskutiert.
    Notes: Summary Miehaelis-constants and enzyme activities for dehydrogenation and transamination of the three branched chainα-keto acids in liver, kidney, skeletal muscle, and brain of rats are reported. After oral load only 11–22 % of the keto acids pass the liver unchanged. Blood levels in pharmacokinetic and absorption studies are related to the Michaelis-constants. At the low keto-acid concentrations after oral application, dehydrogenation in the non-hepatic tissues is supposed to prevail over transamination. Data on feed efficiency of branched chain α-keto acids reported in the literature support this view. The chance for transamination is better after intravenous administration. The transferability of our data to humans, and various factors influencing the efficiency of branched chain α-keto acids are discussed in connection with data reported in the literature.
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    Human vitamin C requirements (1987)
    Springer
    European journal of nutrition 26 (1987), S. 125-137 
    Details
    ISSN: 1436-6215
    Keywords: vitamin C ; functions ; kinetics ; pool ; saturation ; requirements ; RDA
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition , Medicine
    Description / Table of Contents: Zusammenfassung Die Bedeutung von Vitamin C für den menschlichen Organismus wird aus den wichtigen Funktionen ersichtlich, an denen das Vitamin beteiligt ist, wie zum Beispiel Kollagen- und Karnitinsynthesen. In neuerer Zeit entdeckt wurde seine Rolle bei der Noradrenalinsynthese, der Inaktivierung von freien Radikalen sowie der Verhinderung der Nitrosaminbildung. Die Vielfalt dieser Vitamin-C-abhängigen Funktionen läßt erkennen, daß die Bedarfsfestsetzung für Vitamin C nicht nur die Verhütung der Mangelkrankheit Skorbut anvisieren, sondern auch berücksichtigen sollte, daß alle diese Funktionen jederzeit genügend Vitamin C zur Verfügung haben müßten, um optimal reagieren zu können. Das Konzept der Gewebesättigung kommt diesem Ziel am nächsten. Studien mit einem kinetischen Modell haben ergeben, daß eine Sättigung mit täglicher Einnahme von 100 mg Vitamin C bei Nichtrauchern und von 140 mg bei Rauchern eintritt, Mengen, die als optimale Werte gelten können. Bei verschiedenen Krankheiten dürfte der Bedarf höher sein; die genauen Mengen müssen jedoch erst noch ermittelt werden.
    Notes: Summary The importance of vitamin C is reflected in its multifunctional roles which include participation in collagen and carnitine syntheses, promotion of iron absorption and the more recently discovered participation in noradrenaline synthesis, inactivation of free radical chain reactions, prevention of N-nitroso compound formation and more. Given the many extra-antiscorbutic functions of the vitamin, the Recommended Dietary Allowances (RDA) should not just prevent deficiency disease but should aim at providing sufficient amounts for all vitamin C-dependent functions to operate at full capacity. The concept of vitamin C tissue saturation is best able to meet this demand. The use of kinetic models has shown that the body pool is saturated with a daily intake of 100 mg vitamin C in non-smokers and 140 mg in smokers, amounts that may be regarded as optimal RDA values. Certain disease states may be accompanied by still higher vitamin C requirements but the exact amounts are not yet known.
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    Polymerization of acrylamide initiated by Ce(IV)-lactic acid redox system (1983)
    Springer
    Colloid & polymer science 261 (1983), S. 188-189 
    Details
    ISSN: 1435-1536
    Keywords: Polymerization ; kinetics ; redox polymerization ; acrylamide
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF01410701
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    On the theory of photoadsorption kinetics of a-Se colloids: The thermal activation energy and compensation effect (1988)
    Springer
    Colloid & polymer science 266 (1988), S. 958-964 
    Details
    ISSN: 1435-1536
    Keywords: a-Se colloids ; photoadsorption ; kinetics ; activation energy ; compensation effect
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract In this study, a model is developed to explain in microscopic terms the results obtained from thermally activated photoadsorption experiments in a-Se colloids. The observed compensation effect can be described for two different cases. At low efficiency adsorption, the process is controlled by the potential at the boundary layer. In the high efficiency adsorption case, the process is controlled by diffusion transport.
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    Influence of specimen thickness on isothermal crystallization kinetics. A theoretical analysis (1984)
    Springer
    Colloid & polymer science 262 (1984), S. 366-373 
    Details
    ISSN: 1435-1536
    Keywords: kinetics ; isothermal crystallization ; polymer ; spherulite ; differential scanning calorimetry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract In the DSC technique, isothermal crystallization experiments are usually performed on thin flat specimens, but their interpretation generally uses theories developed for an unbounded volume. In this paper, isothermal crystallization of spherical entities in the volume limited by two parallel infinite planes is considered. Our model, derived from Avrami's theory, gives an analytical expression for the transformed volume fraction as a function of time. It is shown that the influence of thickness becomes important when thickness becomes of the order of or smaller than the average spherulite radius. The main effects of a decreasing thickness are a slower crystallization kinetics and a decrease in the Avrami exponent. These results can be used to interpret experimental data obtained in isothermal polymer crystallization.
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    Laser temperature jump experiments with fluorescence polarization and turbidity detection on the phase transition of single shell vesicles of dimyristoylphosphatidylcholine (1985)
    Springer
    Colloid & polymer science 263 (1985), S. 484-493 
    Details
    ISSN: 1435-1536
    Keywords: Phospholipid bilayer ; kinetics ; laser temperature jump ; phase transition
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The iodine-laser temperature-jump technique has been used to investigate the main phase transition in single shell vesicles of dimyristoylphosphatidylcholine. The probe molecules DPH and TMA-DPH were incorporated into the lipid bilayer and laserT-jump experiments with turbidity and flourescence polarization detection were performed. We found three well separated relaxation processes between 5 μs and 10 ms. The relaxation signals showed strong cooperativity in the relaxation times as well as in their corresponding amplituedes. We attributed the relaxation to the formation and dissolution of clusters of different order inside the bilayer.
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    Radical desorption in the emulsion polymerisation of vinyl monomers (1987)
    Springer
    Colloid & polymer science 265 (1987), S. 58-64 
    Details
    ISSN: 1435-1536
    Keywords: Polymerisation ; emulsion ; styrene ; methylmethacrylate ; 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
    Notes: Abstract The dependence of emulsion polymerisation rates on a number of important parameters is considered. Attention is paid to the use of seeded emulsion systems for the evaluation of radical desorption coefficients (k o). Experimental conditions are shown to be important. When the average number of radicals per particle is low, large changes in the rate coefficient for chain termination do not have a large effect on the kinetics. With styrene and methylmethacrylate, radical re-absorption by the polymer particles is shown to be important and radical capture efficiences can be high. Consistency is established between the results of a number of workers and values fork o are shown to be lower than those calculated from chain transfer rates.
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    The effect of TiO2 on the kinetics of polyamide 6 crystallization (1983)
    Springer
    Colloid & polymer science 261 (1983), S. 621-625 
    Details
    ISSN: 1435-1536
    Keywords: Polyamide 6 ; crystallisation ; kinetics ; titania
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The kinetics of isothermal and nonisothermal crystallization of polyamide-6 (PA6) containing titania was studied by means of DSC. It was found thatTiO 2 causes an acceleration in the crystallization of polyamide-6 and lowers the value of the Avrami exponent,n. The presence of TiO2 does not affect equilibrium melting pointT m 0 , glass temperatureT g, or surface free energiesσ e andσ of the basal and lateral surfaces.
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    Proceedings: Ad Hoc Mathematical Fire Modeling Working Group (1984)
    Springer
    Fire technology 20 (1984), S. 47-63 
    Details
    ISSN: 1572-8099
    Keywords: Extinguishment ; fire modeling ; mass loss ; heat release ; char ; reflash ; sprinklers ; radiant flux ; kinetics ; reaction rate ; heat loss ; ash ; latent heat ; spray density ; extinguishing agents
    Source: Springer Online Journal Archives 1860-2000
    Topics: Architecture, Civil Engineering, Surveying
    Notes: Abstract The Ad Hoc Mathematical Fire Modeling Working Group was organized about seven years ago to facilitate voluntary cooperation and coordination in developing mathematical fire modeling capability. The group has a steering committee of representatives of agencies that support fire modeling and related research. These include the National Bureau of Standards' Center for Fire Research, Factory Mutual Research Corp., the Naval Research Laboratory, NASA, and the Federal Aviation Agency. The Group holds plenary meetings when it seems desirable to do so (about once each 1 1/2 years), and workshops on topical subjects. Three workshops were held in 1983. Normally, Group meetings are held before or after other meetings at which a number of interested personnel would likely be present. Minutes are mailed to those who attended and to others (including European and Japanese personnel) who have indicated interest. This workshop was arranged by Ron Alpert of Factory Mutual Research Corp. and held at their facilities at Norwood, MA, in November 1983.
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    Effects of pressure on the kinetics of the dehydration of carbonic acid and the hydrolysis of CO2 in aqueous solution (1982)
    Springer
    Journal of solution chemistry 11 (1982), S. 339-346 
    Details
    ISSN: 1572-8927
    Keywords: Carbon dioxide ; hydrolysis ; aqueous solution ; kinetics ; activation volume
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The pressure dependence of the dehydration reaction of H2CO3 was measured in acidic aqueous solution for pressures up to 1 kbar using a high-pressure stopped-flow instrument. The corresponding volume of activation was found to be 6.4±0.4 cm3-mol−1 at 25°C and 0.5 ionic strength. Volume equation calculations result in a value of −9.9±1.9cm3-mol−1 for the volume of activation for the hydrolysis of CO2 under the same conditions. For the first time, the reaction mechanism can be interpreted in terms of dissociative and associative modes, respectively. These data are used to construct an overall reaction volume profile.
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    Thermodynamic parameters of coupled chemical reactions from temperature jump relaxation amplitudes (1981)
    Springer
    Journal of solution chemistry 10 (1981), S. 39-50 
    Details
    ISSN: 1572-8927
    Keywords: Temperature jump ; kinetics ; thermodynamics ; TRIS ; iminodiacetic acid ; magnesium ion ; phenol red
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Equations describing the temperature jump amplitudes associated with a system of two coupled reactions (TRIS-phenol red) as well as the ternary system (Mg2+-iminodiacetic acid-phenol red) are presented. The termodynamic parameters calculated from experimentally measured temperature perturbation amplitudes using a multiparametric curve fitting procedure are found to be in good agreement with those determined from pH- and costant rate thermometric titrations. For phenol red, pK I =7.55, ΔH I =3.45 kcal, and for Mg2+ iminodiacetic acid, log K M =2.84, ΔH M =3.25 kcal, were obtained. It is shown that this method can be used to determine accurate thermodynamic enthalpy changes over a narrow temperature interval of less than 1.0°C from a single experiment requiring about 50 μl of sample solution.
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    Rate and thermodynamic studies of the interaction between water and iso-butyl cellosolve by ultrasonic methods (1983)
    Springer
    Journal of solution chemistry 12 (1983), S. 771-781 
    Details
    ISSN: 1572-8927
    Keywords: Ultrasonics ; kinetics ; aqueous solution ; iso-butyl cellosolve
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Ultrasonic absorption and velocity measurements in aqueous solution of iso-butyl cellosolve (ethylene glycol iso-butyl ether) as a function of the concentration are reported. The two relaxational absorptions have been attributed to the perturbation of the equilibria expressed by AB⇌A+B and Aα(1/n)An where A is the solute, B is the solvent, AB is the complex and A n is the solute aggregate. The rate constants for each step have been determined. From the concentration dependence of the maximum excess absorption per wave length, the enthalpy change and the volume change for the reaction between the solute and the solvent have been determined for aqueous solutions of butyl cellosolve (ethylene glycol n-butyl ether), iso-butyl cellosolve and propyl cellosolve (ethylene glycol n-propyl ether). The results are consistent with a hydrogen bonding reaction. The effect of the ethers on water structure are considered and it is clear that the fraction of water molecules which can hydrogen bond to the solute decreases with the increasing hydrophobicity of the solute.
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    The kinetics of the solvolysis of chloropentacyanocobaltate(III) ions in water containing 2-methoxyethanol or diethylene glycol: A contrast with the effect of more hydrophobic cosolvents (1994)
    Springer
    Journal of solution chemistry 23 (1994), S. 1089-1100 
    Details
    ISSN: 1572-8927
    Keywords: Solvolysis ; kinetics ; aqueous solvent mixtures ; Co(III) complexes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of the solvolysis of [Co(CN)5Cl]3− have been investigated in water +2-methoxyethanol and water + diethylene glycol mixtures. Although the addition of these linear hydrophilic cosolvent molecules to water produces curvature in the variation of log(rate constant) with the reciprocal of the dielectric constant, their effect on the enthalpy and entropy of activation is minimal, unlike the effect of hydrophobic cosolvents. The application of a Gibbs energy cycle to the solvolysis in water and in the mixtures using either solvent-sorting or TATB values for the Gibbs energy of transfer of the chloride ion between water and the mixture shows that the relative stability of the emergent solvated Co(III) ion in the transition state compared to that of Co(CN)5Cl3− in the initial state increases with increasing content of cosolvent in the mixture. By comparing the effects of other cosolvents on the solvolysis, this differential increase in the relative stabilities of the two species increases with the degree of hydrophobicity of the cosolvent.
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    The effects of aqueous solvent structure on the mutarotation kinetics of glucose (1977)
    Springer
    Journal of solution chemistry 6 (1977), S. 203-216 
    Details
    ISSN: 1572-8927
    Keywords: Glucose ; kinetics ; mixed solvent ; kinetic isotope effect ; enthalpy of activation ; entropy of activation ; tetrahydrofuran ; tert-butanol ; mutarotation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The mutarotation rates of glucose in aqueous mixtures of tetrahydrofuran andtert-butanol in the mole fraction (xi) range 0〈xi〈0.2 have been measured at 5° intervals in the range 5–35°C. The kinetic deuterium isotope effects have been determined for the same solvent compositions at 25 and 35°C. A statistical analysis of the Arrhenius plots indicates that the experimental errors, although small, are too large for the establishment of any compensation behavior between ΔH
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    Kinetics and mechanism of MnO2 dissolution in H2SO4 in the presence of pyrite (1999)
    Springer
    Journal of applied electrochemistry 29 (1999), S. 191-200 
    Details
    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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    URL: http://dx.doi.org/10.1023/A:1003490810114
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    Molecular structure of trans-[Co(NH3)4(NH2CH3)Cl](ClO4)2 (1998)
    Springer
    Journal of chemical crystallography 28 (1998), S. 69-72 
    Details
    ISSN: 1572-8854
    Keywords: Co(III) complex ; crystal structure ; kinetics ; steric effects
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract The title compound crystallizes in the orthorhombic space group Pnma, with a = 7.9209(5), b = 9.818(1), c = 16.867(2) Å, and Z = 4. The structure was solved employing 1864 independent x-ray reflections with I〉2σ(I) by Patterson and difference Fourier techniques and refined by full-matrix least-squares to R = 0.036. The trans-[CO(NH3)4(NH2CH3)Cl](ClO4)2 molecule is on a crystallographic mirror plane. The cobalt ion is in an elongated octahedral coordination with four equatorial ammonia ligands [average Co–N distance equal to 1.966(2) Å], an axial methylamine [Co–N=1.965(3)Å], and an axial chlorine ion [Co–Cl=2.2771(9)Å]. Kinetic steric effects of the complex are interpreted in terms of structural results.
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    URL: http://dx.doi.org/10.1023/A:1021786804676
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    Kinetics of the solvolysis oftrans-dichlorotetra-(4-t-butylpyridine)-cobalt(III) ions in water +t-butyl alcohol mixtures (1990)
    Springer
    Journal of solution chemistry 19 (1990), S. 1073-1084 
    Details
    ISSN: 1572-8927
    Keywords: Solvolysis ; kinetics ; mixtures of water+cosolvent
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Rates of solvolysis of the complex cation [Co(4tBupy)4Cl2]+ have been determined in mixtures of water with the hydrophobic solvent, t-butyl alcohol. The solvent composition at which the extremum is found in the variation of the enthalpy ΔH* and the entropy ΔS* of activation correlates well with the extremum in the variation of the relative partial molar volume of t-butyl alcohol in the mixture and the straight line found for the variation of ΔH* with ΔS* is coincident with the same plot for water + 2-propanol mixtures. A free energy cycle is applied to the process initial state (C n+) going to the transition state [M(n+1)+...Cl−] in water and in the mixture using free energies of transfer of the individual ionic species, ΔG t o (i), from water into the mixture. Values for ΔG t o (i) are derived from the solvent sorting method and from the TATB/TPTB method: using data from either method, changes in solvent structure on going from water into the mixture are found to stabilize the cation in the transition state, M(n+1)+, more than in the initial state, C n+. This is compared with the application of the free energy cycle to the solvolysis of complexes [Co(Rpy)4Cl2]+ and [Coen2LCl]+ in mixtures of water with methanol, 2-propanol or t-butyl alcohol: the above conclusion regarding the relative stabilization of the cations holds for all these complexes in their solvolyses in water+alcohol mixtures using values of ΔG t o (Cl−) from either source.
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    The role of solvent structure in ligand substitution and solvent exchange at some divalent transition-metal cations (1973)
    Springer
    Journal of solution chemistry 2 (1973), S. 217-238 
    Details
    ISSN: 1572-8927
    Keywords: Cation ; energies ; H. S. Frank ; M. Eigen ; R. G. Wilkins ; kinetics ; ligand substitution ; mechanism ; mixed solvents ; nonaqueous ; solvation ; solvent ; solvent structure ; solvent exchange ; transition metal
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The role of the solvent in reactions involving ions is considered in relation to the structure of liquids. The rate constants and activation parameters for ligand substitutions at divalent transition metal cations in various solvents are compared with those for solvent exchanges. The differences are related to structural properties of the solvents, represented by their heats of evaporation and fluidities, and interpreted with the aid of a model developed from that of Frank and Wen. Water is not a typical solvent.
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    Effect of ionic interactions on the rates of reduction of Cu(II) with H2O2 in aqueous solutions (1992)
    Springer
    Journal of solution chemistry 21 (1992), S. 1271-1287 
    Details
    ISSN: 1572-8927
    Keywords: Cu(II) ; kinetics ; reduction ; temperature dependence ; H2O2, NaCl, NaBr, NaClO4
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The rates of reduction of Cu(II) with H2O2 have been measured in NaCl and NaBr solutions and mixtures with NaClO4 as a function of pH (6 to 9), temperature (5 to 45°C) and ionic composition (0.1 to 6M). The effect of pH on the rates was found to be independent of temperature and ionic composition. The rates increased as a function of [H+] raised to the power of 1.3 to 1.6. Speciation calculations indicate that this pH dependence can be attributed to Cu(OH)2 being the reactive species. The rate constants in NaCl and NaBr and mixtures with NaClO4 were independent of ionic strength, but proportional to the halide concentration raised to the power of 2.0 (0.2 to 2.6M). These results can be attributed to Cu(OH)2Cl 2 2− being the reactive species to reduction with H2O2. The Cu(I) halide complexes formed from the reduction are not easily oxidized with O2 or H2O2. The faster rates in Br− solutions, which form stronger complexes with Cu+, support this contention. Measurements made in NaCl with added NaHCO3, NaB(OH)4 EDTA, NTA and glycine were also made. These measurements indicate that the CuL complexes (L=B(OH) 4 − , CO 3 2− , EDTA, NTA, and glycine) are not very reactive to reduction with H2O2. The addition of Mg2+ or Ca2+ caused the rates to increase due to the formation of MgL or CaL complexes and the resultant release of reactive Cu2+.
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    Thermodynamics of coupled reactions by the method of dynamic titration: the Nickel(II)-salicylate ion system (1994)
    Springer
    Journal of solution chemistry 23 (1994), S. 483-500 
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    ISSN: 1572-8927
    Keywords: Thermodynamics ; kinetics ; chemical relaxation ; temperature-jump ; amplitudes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Amplitudes of chemical relaxation signals can provide useful information as to the thermodynamics of coupled chemical reactions. The temperature-jump technique has been used to investigate the thermodynamic behavior of the Nickel(II)-3,5-dinitrosalicylate system in buffer solution, where complex formation steps are coupled to proton transfer steps. The analysis of the relaxation curves is based on the transformation of a set of coupled elementary reactions into a set of uncoupled ‘normal reactions.’ By analogy with classical titrations, the experiments have been performed by changing the metal ion concentration at constant ligand concentration and pH. Each measured amplitude is associated in this way to a point of a ‘dynamic titration’ and a procedure is formulated by which the values of the equilibrium constants and enthalpies of the normal reactions are simultaneously obtained by simple linear plots. From the dependence of these parameters on suitable functions of the concentrations of the reactants the values of ΔG° and ΔH° of the individual steps are derived. It is shown that the addition of a buffer (instead of an indicator) influences the stoichiometric coefficients of the normal reaction in such a way that measurable amplitudes are produced in systems that, as the presently investigated, in unbuffered solution would remain insensitive to the external perturbation. The circumstances under which the dynamic method offers advantages over the classical techniques are discussed.
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    Solvent effects on the acid-catalyzed hydrolysis of tetramethylurea (1976)
    Springer
    Journal of solution chemistry 5 (1976), S. 163-169 
    Details
    ISSN: 1572-8927
    Keywords: Solvent effects ; tetramethylurea ; hydrolysis ; hydrogen bonding ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Tetramethylurea was hydrolyzed in aqueous hydrochloric acid at temperatures of 80, 90, and 100°C. All reactions were carried out in an excess of both tetramethylurea and water, with first-order dependence on acid concentration being observed. As the concentration of water was increased, the rate of hydrolysis decreased until equimolar amounts of water and tetramethylurea were present. Subsequent addition of water had no effect on the observed rate.
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    Sensitivity of PSA process performance to input variables (1995)
    Springer
    Adsorption 1 (1995), S. 133-151 
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    ISSN: 1572-8757
    Keywords: PSA process ; sensitivity ; equilibria ; kinetics ; heats
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract Mathematical models for pressure swing adsorption (PSA) processes essentially require the simultaneous solutions of mass, heat and momentum balance equations for each step of the process using appropriate boundary conditions for the steps. The key model input variables needed for estimating the separation performance of the process are the multicomponent adsorption equilibria, kinetics and heats of adsorption for the system of interest. A very detailed model of an adiabatic Skarstrom PSA cycle for production of high purity methane from a ethylene-methane bulk mixture is developed to study the sensitivity of the process performance to the input variables. The adsorption equilibria are described by the heterogeneous Toth model which accounts for variations of isosteric heats of adsorption of the components with adsorbate loading. A linear driving force model is used to describe the kinetics. The study shows that small errors in the heats of adsorption of the components can severely alter the overall performance of the process (methane recovery and productivity). The adsorptive mass transfer coefficients of the components also must be known fairly accurately in order to obtain precise separation performance.
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    Frequency response analysis of a closed diffusion cell with two resonators (1996)
    Springer
    Adsorption 2 (1996), S. 265-277 
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    ISSN: 1572-8757
    Keywords: frequency response ; diffusion cell ; kinetics ; diffusion ; heat effects
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract This paper deals with frequency response (FR) analysis of a closed diffusion cell system with two resonators, that is both the LHS and RHS volumes are modulated. The analysis is made for a homogeneous particle described by a single effective diffusivity as well as a biporous pellet described by macropore and micropore diffusions. It is shown that if the perturbation of the volume of the reservoir #2 is lagged behind that of the reservoir #1 by 3π/2, the pressure response in reservoir #1 is significantly enhanced with larger amplitude as well as phase angle. When the perturbations of the two reservoirs are out of phase, the heat effect is reduced and can become insignificant when the two perturbations are completely out of phase (ψ = π). Under such a condition, the pressure difference between the two reservoirs could be doubled. In the case of biporous pellets, it is shown that the FR behaviours obtained for micropore diffusion control and macropore diffusion control are well distinguished. In the former case, the FR system reduces to a traditional batch adsorber one while in the latter case, the FR behaviour is the same as for a two resonator system with homogeneous particles. This difference can be used for the discrimination of micropore and macropore diffusion processes.
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    Equilibria and kinetics characterisation of two different structured nutshell-derived activated carbons (1997)
    Springer
    Adsorption 3 (1997), S. 267-275 
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    ISSN: 1572-8757
    Keywords: characterisation ; equilibria ; kinetics ; micropore size distribution ; n-butane ; nutshell
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract Adsorption equilibria and dynamics ofn-butane on two activated carbon samples prepared from the physical activation of nutshell are studied in this paper. The micropore size distribution (MPSD) is considered as the main source of solid heterogeneity. Lennard-Jones' potential theory and Dubinin's theory (TVFM) are used in the equilibria data to derive the MPSD, which is well fitted by a Gamma distribution function. The adsorption energy distribution derived from the MPSD is very asymmetric for both the samples studied, and this energy distribution used in the HMSD/HMSMD kinetics models for the study of adsorption dynamics ofn-butane.
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    Factors affecting bioleaching kinetics of sulfide ores using acidophilic micro-organisms (1999)
    Springer
    BioMetals 12 (1999), S. 1-10 
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    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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    A method to determine the relative value of the barriers of carbon chain growth and termination in Fischer-Tropsch synthesis: elementary reaction kinetics for chain growth (1993)
    Springer
    Catalysis letters 19 (1993), S. 93-97 
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    ISSN: 1572-879X
    Keywords: Fischer-Tropsch synthesis ; reaction activation barrier ; carbon chain growth and termination ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A method is established, by which the difference of the reaction activation barriers of carbon chain growth and termination in Fischer-Tropsch (FT) synthesis can be determined from experiments. A FT synthesis is carried out on Fe/Zn catalyst. We apply the method to analyze the experimental result and obtain the difference of reaction activation barriers of carbon chain growth and termination of α-olefins on the catalyst.
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    The dissociation kinetics of H2S over an alumina supported Co-Mo sulphide catalyst (1996)
    Springer
    Catalysis letters 37 (1996), S. 167-172 
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    ISSN: 1572-879X
    Keywords: dissociation ; kinetics ; Co-Mo sulphide ; H2S
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract In this study, a high surface area 4Co∶6Mo∶100γ-Al2O3 sulphide prepared using precipitation from homogeneous solution (PFHS) has been used for the catalytic splitting of hydrogen sulphide into H2 and elemental sulphur. The activity of this new formulation was significantly better than previously reported recipes. Kinetic data collected over a wide range of H2S partial pressures between 883 and 983 K revealed that, although the decomposition followed a first-order law, a mechanism involving H2S adsorption on co-ordinative unsaturation sites of the Co-Mo sulphide catalyst gave a Langmuir-Hinshelwood rate expression that yielded satisfactory model parameters. In particular, the scission of the surface H-S bond appeared to be the rate determining step.
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    Kinetics and mechanisms of the low-temperature degradation of cellulose (1994)
    Springer
    Cellulose 1 (1994), S. 26-56 
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    ISSN: 1572-882X
    Keywords: low-temperature degradation ; kinetics ; mechanisms ; electrical insulation ; transformers
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract A critical review is given of the degradation of cellulose in the low-temperature region (below about 300°C) of power transformer operation. The large number of kinetic studies, under a variety of environmental conditions from Kraft paper in insulating oil, to cotton and paper in oxygen, are considered in terms of a first-order polymer chain scission model. In many cases, the data are replotted to suit the model. A common activation energy of 111±6 kjmol−1 is calculated and it is shown that the pre-exponential factor, rather than the activation energy, is sensitive to the oxidizing nature of the environment and the susceptibility to degradation of the material. The chemical mechanisms of degradation are reviewed, and conclusions and recommendations are made regarding chemical condition monitoring and life prediction of electrical insulation.
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    Why Does the Linear Driving Force Model for Adsorption Kinetics Work? (2000)
    Springer
    Adsorption 6 (2000), S. 137-147 
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    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.
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    Effect of potassium on the high pressure kinetics of ammonia synthesis over fused iron catalyst (1996)
    Springer
    Catalysis letters 37 (1996), S. 173-179 
    Details
    ISSN: 1572-879X
    Keywords: ammonia synthesis ; iron catalysts ; potassium promotion ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Measurements were performed of reaction rate in the process of ammonia synthesis (T=370–470°C) on doubly promoted (DP) (Al2O3, CaO) and triply promoted (TP) (K2O, Al2O3, CaO) iron catalysts. The latter were obtained by impregnation of the reduced and subsequently passivated DP precursors with alcoholic solution of KOH. The studies were carried out under high total pressure (10 MPa) in a wide range of ammonia partial pressure in the gas phase: from 0.25 to about 7 bar. The results are shown to be authoritative for the so-called kinetic regime. The effect of the presence of K+ cations in the catalyst was the stronger, as the temperature of the reaction was the lower and, in particular, the ammonia pressure in the gas phase the higher. The obtained results are in good accordance with the results of Somorjai's studies on activity of iron single crystal surfaces both clean and covered with (K+O) adlayer.
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    Oxidation of carbidic carbon on a rhodium surface (1994)
    Springer
    Catalysis letters 27 (1994), S. 79-90 
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    ISSN: 1572-879X
    Keywords: kinetics ; carbon ; oxygen ; recombination ; rhodium ; surface characterisation ; XPS ; AES
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Different mechanisms of atomic carbon and oxygen recombination on a rhodium surface are studied with Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS). The kinetics of adsorbed carbidic carbon oxidation (carbon coverageθ c ≈ 0.1–0.3 ML) by gas-phase oxygen that proceeds by a Langmuir-Hinshelwood reaction mechanism, provides the value of the activation energy for recombination (E rec ⇂t ≈ 170±20 kJ/mol).E rec ⇂t depends slightly on the carbon coverage. An Eley-Rideal type of reaction was observed for adsorbed oxygen and atomic gas-phase carbon recombination which occurs in a dynamic regime. The low value found for the activation energy (near zero) is consistent with the mechanism that this exothermic reaction is too fast for energy dissipation into the substrate; the energy is mainly transferred into translational, vibrational and rotational energy of CO.
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    Effect of K, Cs and Ba on the kinetics of NH3 synthesis over carbon-based ruthenium catalysts (2000)
    Springer
    Catalysis letters 68 (2000), S. 163-168 
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    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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    Prediction of paper permanence by accelerated aging II. Comparison of the predictions with natural aging results (1996)
    Springer
    Cellulose 3 (1996), S. 269-279 
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    ISSN: 1572-882X
    Keywords: accelerated tests ; aging tests ; cellulose degradation ; durability ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract Accelerated aging tests are credible and useful to predict paper permanence only if such tests can be shown to correlate with natural aging. In the first part of this study, a kinetic model was developed based on the accelerated aging results. In this report, we have shown that this kinetic model can indeed predict the natural aging results of lignin-free sheets with a statistical confidence. This is the first quantitative comparison of accelerated aging with natural aging.
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    Reaction Between Copper Nitrate Hydrate and Methoxydimethyloctylsilane in Methanol (1998)
    Springer
    Journal of solution chemistry 27 (1998), S. 1123-1138 
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    ISSN: 1572-8927
    Keywords: Sol–gel processing ; hydrolysis ; condensation ; kinetics ; methoxydimethyloctylsilane ; copper nitrate hydrate ; phase diagram
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The reaction rate was determined for copper nitrate hydrate with methoxydimethyloctylsilane (MDOS) in methanol. The rate constants of hydrolysis and condensation were established by quantitative measurement of the product and Karl Fischer water determination. The reaction with the hydrated copper salt resulted in the phase separation of an insoluble product from the reaction mixture. The structure of the product was determined, by Fourier Transform Infrared Spectrometry (FTIR) and Nuclear Magnetic Resonance (NMR) to be a dimer of the MDOS. The results showed the alcohol, producing condensation reaction was negligible in the formation of the dimer. contrary to the case for the well-known reaction by trialkoxysilanes and tetraalkoxysilanes.
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    Enthalpies of reaction and reaction rates by flow microcalorimetry: Ester hydrolysis in basic medium (1980)
    Springer
    Journal of solution chemistry 9 (1980), S. 59-73 
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    ISSN: 1572-8927
    Keywords: Enthalpies of reaction ; heats of reaction ; kinetics ; ester hydrolysis ; microcalorimetry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The conditions under which the Picker flow microcalorimeter can be used to measure enthalpies and rates of reactions were investigated. For this purpose, systematic studies were made of the enthalpies of neutralization of HCl, HBr, HNO 3 , acetic, proprionic, and butyric acids with NaOH, enthalpies of hydrolysis of methyl and ethyl acetate with NaOH, and the reaction rates of the ester hydrolysis with NaOH. The general procedure and various sources of error are discussed and it is concluded that enthalpies of slow reactions can be measured to about 1% when the calorimeter is operated in the quasi-isothermal mode and the reaction rates to about 3% when operated in the quasi-adiabatic mode.
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    On the kinetics of degradation of cellulose (1997)
    Springer
    Cellulose 4 (1997), S. 1-5 
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    ISSN: 1572-882X
    Keywords: paper ; degradation ; ageing ; kinetics ; modelling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition , Process Engineering, Biotechnology, Nutrition Technology
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    URL: http://dx.doi.org/10.1023/A:1018408515574
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    Prediction of paper permanence by accelerated aging I. Kinetic analysis of the aging process (1996)
    Springer
    Cellulose 3 (1996), S. 243-267 
    Details
    ISSN: 1572-882X
    Keywords: aging tests ; cellulose degradation ; durability ; kinetics ; paper properties
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract The validity of accelerated aging tests to predict and rank papers on their permanence has been under question, preventing the development of performance-based standards for permanent paper. We conducted a general kinetic analysis to investigate the aging process of paper. A general kinetic model is proposed to describe the depolymerization of cellulose. Experimentally it was shown that in the case of aging, cellulose degradation follows classic first-order kinetics as a special case of our general kinetic model. The Arrhenius equation was critically re-examined for the case of a multiple reaction system. It was shown analytically that the Arrhenius equation is still applicable when certain conditions are met. This was convincingly supported by experimental results. We also analysed the dependence of the degradation rate on the moisture content and hydrogen ion concentration. By conducting systematic experiments on these two factors, a general and quantitative relationship was established to explain the contribution of each factor and their interactions. Finally, based on this kinetic analysis, the effects of storage conditions on the life expectancy of paper were estimated.
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    URL: http://dx.doi.org/10.1007/BF02228805
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    A correlation of gas solubilities and kinetics of hydrolysis in binary aqueous mixtures (1974)
    Springer
    Journal of solution chemistry 3 (1974), S. 881-887 
    Details
    ISSN: 1572-8927
    Keywords: Binary aqueous mixtures ; solubilities ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A treatment which predicts the solubilities of gases in solvent mixtures is examined in the context of the analysis of kinetic data for reactions in aqueous mixtures. The treatment is qualitatively successful to some extent in resolving the effects of changes in the initial state of the reacting substrate in the activation parameters.
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    URL: http://dx.doi.org/10.1007/BF00647942
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    Reaction Kinetics for the Anionic Ring-Opening Polymerization of Tetraphenyltetramethylcyclotetrasiloxane Using a Fast Initiator System (1998)
    Springer
    Journal of inorganic and organometallic polymers and materials 8 (1998), S. 111-117 
    Details
    ISSN: 1572-8870
    Keywords: Organosiloxane ; kinetics ; poly(phenylmethylsiloxane) ; catalyst ; anionic ; ring-opening
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract It is well known that the rate of polymerization for an anionic mechanism is dependent on the ability of the bulk material or solvent system to disassociate the ion pair at the propagating chain end. In the anionic ring-opening polymerization of cyclic organosiloxanes in particular, the larger and softer the counter ion, the more rapidly the reaction proceeds. A recently developed phosphazene initiator system provides a large, soft counter ion relative to other traditional initiators used for the polymerization of poly(dimethylsiloxane) (PDMS). This novel initiator system was used in this investigation for the ring-opening polymerization of tetraphenyltetramethylcyclotetrasiloxane (P4) and the reaction kinetics under bulk and solution conditions were investigated. The new initiator system showed a dramatic increase in the rate of polymerization over the conventional potassium hydroxide-catalyzed system. Furthermore, this initiator was sufficiently reactive to be useful for the ring-opening polymerization of P4 at 293 K.
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    URL: http://dx.doi.org/10.1023/A:1022487906770
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    Degradation of Cellulosic Materials Under the Alkaline Conditions of a Cementitious Repository for Low- and Intermediate-Level Radioactive Waste. II. Degradation Kinetics (1999)
    Springer
    Journal of polymers and the environment 7 (1999), S. 41-51 
    Details
    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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    Ultrasonic absorption of the oxyethylene group in aqueous nonelectrolyte solutions (1986)
    Springer
    Journal of solution chemistry 15 (1986), S. 221-229 
    Details
    ISSN: 1572-8927
    Keywords: Ultrasonics ; kinetics ; aqueous solution ; triethylene glycol monobutyl ether
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The ultrasonic absorption from 6.5 to 220 MHz and velocities at 2.5 MHz have been measured in aqueous solution of triethylene glycol monobutyl ether as a function of concentration at 25°C. A single relaxational excess absorption, observed from 0.60 to 2.5 mol-dm−3, is attributed to a perturbation of an equilibrium associated with solute-solvent interaction. Rate constants for the forward and reverse processes have been determined from the concentration dependence of the relaxation frequency, and the influence on the water structure by an addition of the solute has been considered. Solution densities were also measured in order to obtain the expansivity of the solution. The standard volume and enthalpy changes of the reaction have been estimated from the concentration dependence of the maximum excess absorption per wave length. A linear relationship between the number of oxyethylene groups and the free energy change between bonded water and nonbonded water is established.
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    High resolution NMR techniques in catalysis (1998)
    Springer
    Topics in catalysis 5 (1998), S. 133-147 
    Details
    ISSN: 1572-9028
    Keywords: NMR ; catalysis ; high pressure ; dynamic equilibria ; magnetization transfer ; sapphire tube ; gas phase ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract High resolution NMR techniques are applicable to a variety of aspects of catalysis. Methods for studying homogeneously-catalyzed systems under high gas pressure are described along with approaches for obtaining mechanistic and dynamic information. Many of the same techniques may be applied to heterogeneous catalysis by following the reaction chemistry by gas phase NMR.
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    URL: http://dx.doi.org/10.1023/A:1019133515789
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    Selectivity from a kinetic point of view: nonlinear behavior of logarithmic product ratios as a function of the reciprocal temperature (1998)
    Springer
    Topics in catalysis 5 (1998), S. 159-176 
    Details
    ISSN: 1572-9028
    Keywords: nonlinear temperature behavior ; Eyring plot ; modified Eyring plot ; selectivity ; selection process ; enantioselectivity ; selection level ; isoinversion principle ; isoinversion temperature ; inversion temperature ; kinetics ; catalysis ; asymmetric hydrogenation ; dihydroxylation ; cocyclization
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The influence of the temperature on selectivity is described under special consideration of nonlinearities in the corresponding modified Eyring plots. Reasons for the experimentally well-known behavior are discussed. Furthermore, the conditions for nonlinear temperature behavior are quantified and a concept is described which allows the determination of the temperature dependence of a single reaction pathway in a selection process.
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    Dynamics and self-organization of catalytic systems (1994)
    Springer
    Topics in catalysis 1 (1994), S. 305-314 
    Details
    ISSN: 1572-9028
    Keywords: non-Langmuir ; kinetics ; non-linear dynamics ; oscillations ; chaos ; self-organization
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of a catalytic reaction is frequently formulated in terms of simple concepts of the Langmuir type. Apart from limitations arising from the non-uniformity of the catalyst's surface and from the coverage dependence of the rate “constants”, several other complications may come into play. These may arise on the “quantum level” where energy flow between the various degrees of freedom may cause failure of simple transition state theory, as well as on the “continuum level” where formulation of rate equations in terms of coupled non-linear differential equations may give rise to a rich scenario of spatio-temporal self-organization, including kinetic oscillations, chaos, and formation of concentration patterns. Several of these phenomena are illustrated by selected examples.
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    Mechanism of the hydrodenitrogenation of o-toluidine and methylcyclohexylamine over NiMo/γ-Al2O3 (2000)
    Springer
    Topics in catalysis 11-12 (2000), S. 327-333 
    Details
    ISSN: 1572-9028
    Keywords: hydrodenitrogenation ; toluidine ; methylcyclohexylamine ; kinetics ; nickel-promoted molybdenum sulphide
    Source: Springer Online Journal Archives 1860-2000
    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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    URL: http://dx.doi.org/10.1023/A:1027208200169
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    The lymphatic route. 1) Albumin and hyaluronidase modify the normal distribution of interferon in lymph and plasma (1986)
    Springer
    Cellular and molecular life sciences 42 (1986), S. 432-433 
    Details
    ISSN: 1420-9071
    Keywords: Interferon ; immunomodulator ; catabolism ; pharmacokinetics ; administration routes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary When human recombinant interferon-α2 diluted in saline was injected s.c. into rabbits, the total amount recovered in thoracic lymph was less than 0.4%. Recoveries increased from 2- to 8-fold if interferon was injected in 4% albumin or with hyaluronidase, respectively. Albumin added to interferon acts as an interstitial fluid expander, thus favoring interferon absorption through lymphatics rather than blood capillaries. This strategy may increase the therapeutic index of interferon.
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    URL: http://dx.doi.org/10.1007/BF02118644
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    The polymerization of sickle hemoglobin in solutions and cells (1993)
    Springer
    Cellular and molecular life sciences 49 (1993), S. 110-117 
    Details
    ISSN: 1420-9071
    Keywords: Polymerization ; sickle hemoglobin ; sickle cell disease ; kinetics ; thermodynamics ; polymer domains ; nucleation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Abstract The polymerization of sickle hemoglobin occurs by the same mechanisms in solutions and in cells, and involves the formation of 14 stranded fibers from hemoglobin molecules which have assumed a deoxy quaternary structure. The fibers form via two types of highly concentration-dependent nucleation processes: homogeneous nucleation in solutions with hemoglobin activity above a critical activity, and heterogeneous nucleation in similarly supersaturated solutions which also contain hemoglobin polymers. The latter pathway is dominant, and creates polymer arrays called domains. The individual polymers bend, but also cross-link, and the resulting mass behaves as a solid. The concentration of polymerized hemoglobin increases exponentially unless clamped by rate limiting effects such as oxygen delivery.
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    Sorption Equilibria and Kinetics of Hydrocarbons onto Activated Carbon Samples Having Different Micropore Size Distributions (1999)
    Springer
    Adsorption 5 (1999), S. 25-37 
    Details
    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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    URL: http://dx.doi.org/10.1023/A:1026481704926
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    Static and Kinetic Studies on the Adsorption Behavior of Sulfadiazene (2000)
    Springer
    Adsorption 6 (2000), S. 349-357 
    Details
    ISSN: 1572-8757
    Keywords: sulfadiazene ; adsorption ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    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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    URL: http://dx.doi.org/10.1023/A:1026517117239
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    The influence of sulfur dioxide on propane oxidation activity over supported platinum and palladium (1994)
    Springer
    Catalysis letters 30 (1994), S. 41-51 
    Details
    ISSN: 1572-879X
    Keywords: propane ; oxidation ; platinum ; palladium ; sulfur dioxide ; alumina ; zirconia ; activity ; acidity ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Earlier studies have shown that sulfur dioxide and metal-support interaction can strongly influence propane oxidation over platinum. In particular, oxidation activity is enhanced when platinum is supported on sulfated γ-alumina or zirconia compared to γ-alumina. Therefore, it is of interest to compare the performance of palladium under the same experimental conditions. Four model catalysts were examined: Pt/γ-alumina, Pt/zirconia, Pd/γ-alumina and Pd/zirconia. The metal loading was kept at or below 0.05 wt% to emphasize changes in activity attributable to metal-support interaction. Reaction rates were measured with and without sulfur dioxide. Surface sulfation was analyzed by measuring acid strength and evaluating spectra obtained by Fourier-transform infrared spectroscopy. In contrast to platinum, sulfation does not promote propane oxidation on Pd/γ-alumina, and Pd/zirconia is less active than Pd/γ-alumina.
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    Furfural hydrogenation over carbon‐supported copper (1999)
    Springer
    Catalysis letters 60 (1999), S. 51-57 
    Details
    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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    Study of the ammonia decomposition over iron catalysts (1999)
    Springer
    Catalysis letters 60 (1999), S. 167-171 
    Details
    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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    NO reduction over La2O3 using methanol (2000)
    Springer
    Catalysis letters 64 (2000), S. 65-75 
    Details
    ISSN: 1572-879X
    Keywords: NO reduction ; CH3OH ; La2O3 ; methyl nitrite ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    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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    Pure and Binary Gas Adsorption Equilibria and Kinetics of Methane and Nitrogen on 4A Zeolite by Isotope Exchange Technique (1999)
    Springer
    Adsorption 5 (1999), S. 145-158 
    Details
    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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    Kinetic studies on oxidation of aromatic donor molecules by horseradish peroxidase and lactoperoxidase (1997)
    Springer
    BioMetals 10 (1997), S. 23-26 
    Details
    ISSN: 1572-8773
    Keywords: aromatic donor molecules ; horseradish peroxidase ; kinetics ; lactoperoxidase
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract Based on kinetic evidence, it has been shown for the first time that the mode of binding of aromatic donor molecules is similar in horseradish peroxidase and lactoperoxidase; also that the nature of the heme plays an important role in the reaction with hydrogen peroxide, and has no effect on the reaction of the intermediate compound II with aromatic substrates.
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    Partial hydrogenation of benzene to cyclohexene in a continuously operated slurry reactor (1995)
    Springer
    Catalysis letters 31 (1995), S. 431-438 
    Details
    ISSN: 1572-879X
    Keywords: partial hydrogenation of benzene ; production of cyclohexene ; kinetics ; reaction mechanism ; ruthenium catalyst
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A method has been developed for direct measurement of reaction rates in a continuously operated slurry (CST-) reactor. In contrast to the usual procedure in a two-liquid-phase system the reactor contains only one liquid phase, an aqueous zinc chloride solution in which a ruthenium lanthanoxide catalyst is suspended. The selectivity of benzene hydrogenation with respect to cyclohexene is higher when the new one-liquid-phase procedure is applied. With decreasing degree of benzene conversion the selectivity with respect to cyclohexene approaches 100%. The conclusion is that cyclohexane is formed only by consecutive hydrogenation of cyclohexene.
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    Non-uniform surface kinetics with two types of sites: the case of ethanol oxidation on molybdenum oxide (1996)
    Springer
    Catalysis letters 39 (1996), S. 67-71 
    Details
    ISSN: 1572-879X
    Keywords: non-uniform surface ; kinetics ; ethanol ; oxidation ; molybdenum oxide
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Temkin's theory of rates of catalytic reactions on non-uniform surfaces is extended to the MoO3-catalyzed oxidation of ethanol to acetaldehyde. Two types of sites are assumed to be present, an oxygen atom site that can be modeled with uniform properties and a metal atom site characterized by non-uniform properties both for ethanol chemisorption to an ethoxide intermediate and the conversion of this intermediate to acetaldehyde. The rate-limiting step is the cleavage of a C-H bond in the absorbed ethoxide intermediate. Non-uniform surface kinetics leads to a kinetic rate expression of the form $$v = kP_{C_2 H_5 OH}^{1 - m} P_{O_2 }^{(1 - m)/4} P_{H_2 O}^{ - (1 - m)/2} $$ . Such a rate expression, withm=0.14, is shown to provide a good fit to kinetic data for the selective oxidation of ethanol on a silica supported molybdenum oxide catalyst.
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    Kinetics of the gas-solid heterogeneous photocatalytic oxidation of trichloroethylene by near UV illuminated titanium dioxide (1990)
    Springer
    Catalysis letters 4 (1990), S. 345-354 
    Details
    ISSN: 1572-879X
    Keywords: Ultraviolet heterogeneous photocatalysis ; oxidation ; trichloroethylene ; titania ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Kinetics of the gas/solid heterogeneous photocatalytic oxidation of dilute trichloroethylene (TCE) vapors by ultraviolet-illuminated titanium dioxide have been determined using a fixed-bed dynamic photoreactor. Reaction rate dependences on inlet TCE, oxygen and water vapor concentrations were found to consist of both reactant sensitive and insensitive regions. In the reactant sensitive regions, measured limiting apparent reaction rate orders for TCE, oxygen and water vapor are 0.8, 1.7 and — 3, respectively. Water vapor in the reactant stream lowersinitial reaction rates relative to corresponding water free conditions, but is required to sustain photocatalytic activity for extended periods of time.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00765320
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  • 90
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    Platinum particle size effect on the oxidative dehydrogenation of aqueous ethanol (1996)
    Springer
    Catalysis letters 36 (1996), S. 31-36 
    Details
    ISSN: 1572-879X
    Keywords: ethanol ; kinetics ; oxidation ; oxydehydrogenation ; platinum ; structure sensitivity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The effect of the platinum particle size was investigated for the catalytic oxidative dehydrogenation of aqueous ethanol to ethanal at a temperature of 303 K, an ethanol concentration of 260 mol m−3, a partial oxygen pressure 60 kPa, a pH of 9, and an ethanal and ethanoate concentration of 20 mol m−3. A particle size effect on the turnover frequency was observed but only for particle sizes smaller than 2 nm. Hence, the reaction shows a limited structure sensitivity.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00807202
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  • 91
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    Solvent effects in the kinetics of the enantioselective hydrogenation of ethyl pyruvate (1998)
    Springer
    Catalysis letters 55 (1998), S. 73-77 
    Details
    ISSN: 1572-879X
    Keywords: enantioselectivity ; hydrogenation of ethyl pyruvate ; Pt/alumina catalyst ; solvent effects ; kinetics ; solvent polarity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The influence of solvent on the kinetics of enantioselective hydrogenation of ethyl pyruvate by Pt/Al2O3/dihydrocinchonidine is reported. In a non‐polar solvent, toluene, the reaction is approximately zero order in substrate at constant hydrogen pressure, while under the same conditions and at the same substrate concentration, in the polar solvents ethanol and propylene carbonate the reaction shows a first‐order substrate concentration dependence. Fits to a Michaelis–Menten rate expression show that these differences are the expression of the relative magnitudes of the adsorption term in the rate expression, which in turn reflects the influence of the solvent on the adsorption–desorption processes which take place at the catalyst surface.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1019078727850
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  • 92
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    The detailed kinetics of the desorption of hydrogen from polycrystalline copper catalysts (1999)
    Springer
    Catalysis letters 59 (1999), S. 143-149 
    Details
    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.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1019080823616
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  • 93
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    Oxidation of dicyclopentadiene catalyzed by palladium(II) acetate and p-benzoquinone in the presence of inorganic acid (2000)
    Springer
    Catalysis letters 69 (2000), S. 103-107 
    Details
    ISSN: 1572-879X
    Keywords: dicyclopentadiene ; Wacker oxidation ; Pd(AcO)2 ; benzoquinone ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    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.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1019053402854
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  • 94
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    Temperature-jump FT-IR time-resolved spectrometry (1988)
    Springer
    Microchimica acta 94 (1988), S. 277-278 
    Details
    ISSN: 1436-5073
    Keywords: kinetics ; FT-IR ; temporal resolution
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A system for performing gas-phase rapid scanning Fourier transform infrared time-resolved Spectrometry (FT-IR/TRS) has been evaluated. This technique can be applied to the study of the lifetimes and reactivity of transient species and can provide detailed information regarding reaction rate constants. Temperature-jump experiments have been initiated and preliminary results are presented.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF01205888
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  • 95
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    Dynamic Fourier transform infrared spectroscopy in polymer research (1988)
    Springer
    Microchimica acta 94 (1988), S. 323-328 
    Details
    ISSN: 1436-5073
    Keywords: FTIR spectroscopy ; kinetics ; polymers ; rheo-optics ; variable-temperature measurements
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The rapid-scanning capability of FTIR instrumentation has revitalized the field of vibrational spectroscopy in polymer research and will be discussed with reference to the study of polyurethane kinetics, the temperature dependence of hydrogen bonding in polyamide 6 and strain-induced crystallization in a polydimethylsiloxane elastomer.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF01205899
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  • 96
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    Spectrophotometric determination of mercury with 5,10,15,20-tetrakis(3-chloro-4-sulfophenyl)porphine by flow injection analysis (1994)
    Springer
    Microchimica acta 113 (1994), S. 81-89 
    Details
    ISSN: 1436-5073
    Keywords: flow injection analysis (FIA) ; mercury ; porphyrin ; kinetics ; spectro-photometry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract 5,10,15,20-tetrakis(3-chloro-4-sulfophenyl)porphine (m-Cl-TPPS4) was synthesized and used for the Spectrophotometric determination of mercury by flow injection analysis. A pseudo-first-order reaction kinetic mechanism was proposed with a rate constant of 0.8 min−1 for Hg(II) withm-Cl-TPPS4 in the presence of 8-hydroxyquinoline in a medium of 1.0M acetic acid and sodium acetate buffer solution (pH 6.22). In the optimum conditions of reaction temperature (85 ° C), stopped-flow time (60 s) and sampling volume (100 μl), the method's relative standard deviation was 0.82% (n = 12) at 5.0 μg ml−1 mercury, with a linear range of 0–12.0 μg ml−1 and an analytical frequency of 60h−1. The detection limit (3σ) was 0.025 μg ml−1. Interference studies showed that most metal ions co-existing with Hg2+ could be tolerated at 100-fold excess levels, but Zn2+, Cu2+ and Mn2+ needed to be masked. The method has been applied to the analysis of water samples with satisfactory results.
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    URL: http://dx.doi.org/10.1007/BF01243140
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  • 97
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    Increased sensitivity of an enzyme immunoassay (ELISA) for the determination of triazine herbicides by variation of tracer incubation time (1992)
    Springer
    Microchimica acta 108 (1992), S. 29-40 
    Details
    ISSN: 1436-5073
    Keywords: atrazine ; terbuthylazine ; sequential binding ; kinetics ; cross-reactivity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Immunoassays for triazine herbicides were tested for their reaction to the variation of the tracer incubation time. By application of a sequential technique the measuring range of atrazine could be expanded to five decades and the total duration of the test could be reduced to about 30 min. In an optimized version a lower detection limit of 9 pmol/l (2 ng/l) was achieved. The detection limit of a sensitive immunoassay for terbuthylazine is also below the concentration limit demanded of the German drinking water regulation (100 ng/l) and reaches 130 pmol/l (30 ng/l). Short tracer incubation times did not lead to increased cross-reactivities in contrast to theoretical models [1, 2]. Different mechanisms, which could cause a shift of the center point of the calibration curve, are discussed, including kinetic considerations.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF01240369
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  • 98
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    Improving the performance of the two-rate parameter by use of the integrating ratemeter and temporal optimization (1996)
    Springer
    Microchimica acta 124 (1996), S. 13-25 
    Details
    ISSN: 1436-5073
    Keywords: kinetics ; rates ; integrating ratemeter ; optimization ; first-order
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The integrating ratemeter is used in concert with the two-rate parameter to form the integrating ratemeter two-rate parameter. Propagation of error theory is applied to the integrating ratemeter two-rate parameter to yield expressions for the precision of rates calculated from the integrating ratemeter two-rate parameter in terms of the precision of the rates measured with the integrating ratemeter. Simulations and experimental results show that in cases where the standard deviation of the rate is relatively constant, the optimum time to make a rate measurement using the integrating ratemeter is also the optimum time to measure either of the rates in the two-rate parameter. If either of the two rates comprising the two-rate parameter is measured at the optimum time, then the precision and accuracy of concentrations measured with this technique are optimized.
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    URL: http://dx.doi.org/10.1007/BF01244952
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  • 99
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    Effect of mineral nutrients on the kinetics of methane utilization by methanotrophs (1993)
    Springer
    Biodegradation 4 (1993), S. 163-170 
    Details
    ISSN: 1572-9729
    Keywords: factorial analysis ; kinetics ; methane ; methanotrophs ; nutrients
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Energy, Environment Protection, Nuclear Power Engineering , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract The effect of different mineral nutrients on the kinetics of methane biodegradation by a mixed culture of methanotrophic bacteria was studied. The substrate factors examined were ammonia, iron, copper, manganese, phosphate, and sulphide. The presence of iron in the growth medium had a strong effect on the yield coefficient. Yield coefficients up to 0.49 mg protein per mg methane were observed when iron was added at concentrations of 0.10–5.0 mg/l. Iron addition also increased the maximum methane utilization rate. The same effect was observed after addition of ammonium to a medium where nitrate was the only nitrogen source. The observed Monod constant for methane utilization increased with increasing concentration of ammonia. This shows that ammonia is a weak competitive inhibitor as observed by other researchers. Relatively high levels of both ammonia (70 mg/l) and copper (300 µg/l) inhibited the methane degradation, probably due to the toxic effect of copper-amine complexes.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00695118
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  • 100
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    Transformation kinetics and potential availability of specifically-sorbed phosphate in soils (1998)
    Springer
    Nutrient cycling in agroecosystems 51 (1998), S. 209-215 
    Details
    ISSN: 1573-0867
    Keywords: Desorption ; kinetics ; microbial transformation ; phosphate ; soils
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract The improvement of P management in agriculture and environment requires a good understanding of residual effect of applied P in soils. The specific adsorption of P on variable charge minerals has been considered as the major mechanism that leads to a very low utilization of P fertilizer by crops within a growing season in Chinese red soils. Soil incubation and isotope tracing analysis were carried out to examine the transformation kinetics and potential availability of added specifically sorbed 32P in two pH contrasting light textured soils. The 32P recovered by 0.5 M NaHCO3 extraction and microbial biomass-P measurement from the added specifically sorbed 32P in the soils was well described by a first-order reaction and a Langmuir-type kinetic model, with correlation coefficients (R) being, on average, 0.938 and 0.959, respectively. The half-life (t1/2, from the first-order model) of the four tested mineral-P complexes ranged from 29 to 47 d in the acid sandy soil and 33 to 105 d in the neutral silty soil. Goethite-P was the most stable among the four tested mineral-P complexes. The potential availability of the mineral complex P (q m , in percent of total 32P added) obtained from the Langmuir equation ranged from 43.7 to 90.9% for the four mineral-P complexes, and decreased in the order: Al oxide-P (90.9%) 〉 montmorillonite-P (86.2%) 〉 kaolinite-P (77.5%) 〉 goethite-P (60.2%) in the acid sandy soil, whereas the order was Al oxide-P (89.3%) 〉 kaolinite-P (86.2%) 〉 montmorillonite-P (82.6%) 〉 goethite-P (43.7%) in the neutral silty soil. Based on the release rate and potential availability, kaolinite-P and Al oxide-P could be important sources for residual effect of applied P in variable-charge soils. The goethite-P has the lowest release rate and potential availability among the mineral-P complexes, implying that iron oxides may be the most important variable-charge mineral responsible for P fixation in the Chinese red soils.
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    URL: http://dx.doi.org/10.1023/A:1009749619865
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