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Pressure Data (pressure + data)
Selected AbstractsOn the Analyses of Mixture Vapor Pressure Data: The Hydrogen Peroxide/Water System and Its Excess Thermodynamic FunctionsCHEMISTRY - A EUROPEAN JOURNAL, Issue 24 2004Stanley L. Manatt Dr. Abstract Reported here are some aspects of the analysis of mixture vapor pressure data using the model-free Redlich,Kister approach that have heretofore not been recognized. These are that the pure vapor pressure of one or more components and the average temperature of the complex apparatuses used in such studies can be obtained from the mixture vapor pressures. The findings reported here raise questions regarding current and past approaches for analyses of mixture vapor pressure data. As a test case for this analysis approach the H2O2,H2O mixture vapor pressure measurements reported by Scatchard, Kavanagh, and Tickner (G. Scatchard, G. M. Kavanagh, L. B. Ticknor, J. Am. Chem. Soc.1952, 74, 3715,3720; G. M. Kavanagh, PhD. Thesis, Massachusetts Institute of Technology (USA), 1949) have been used; there is significant recent interest in this system. It was found that the original data is fit far better with a four-parameter Redlich,Kister excess energy expansion with inclusion of the pure hydrogen peroxide vapor pressure and the temperature as parameters. Comparisons of the present results with the previous analyses of this suite of data exhibit significant deviations. A precedent for consideration of iteration of temperature exists from the little-known work of Uchida, Ogawa, and Yamaguchi (S. Uchida, S. Ogawa, M. Yamaguchi, Japan Sci. Eng. Sci.1950, 1, 41,49) who observed significant variations of temperature from place to place within a carefully insulated apparatus of the type traditionally used in mixture vapor pressure measurements. For hydrogen peroxide, new critical constants and vapor pressure,temperature equations needed in the analysis approach described above have been derived. Also temperature functions for the four Redlich,Kister parameters were derived, that allowed calculations of the excess Gibbs energy, excess entropy, and excess enthalpy whose values at various temperatures indicate the complexity of H2O2,H2O mixtures not evident in the original analyses of this suite of experimental results. [source] On the Synthesis of Carbon Nanofibers and Nanotubes by Microwave Irradiation: Parameters, Catalysts, and SubstratesADVANCED FUNCTIONAL MATERIALS, Issue 17 2009Tamara Druzhinina Abstract The microwave (MW)-assisted synthesis of one dimensional carbon systems is introduced as a promising approach to improve the speed and cost-effectiveness of the fabrication process. Improved reaction conditions are generated by direct MW heating and synthesis under advanced reaction conditions. The influence of the reaction conditions is investigated and the importance of individual process parameters on the synthesis is discussed. Temperature and pressure data recorded during the irradiation process are analyzed in detail and allow the determination of essential process parameters. This leads to improved reaction conditions, better control of the one-dimensional carbon nanosystems by tuning the catalyst materials, and allows expanding this approach to initiate the synthesis on a variety of different substrates, such as quartz glass and mica. [source] Hydraulic observations from a 1 year fluid production test in the 4000 m deep KTB pilot boreholeGEOFLUIDS (ELECTRONIC), Issue 1 2006W. GRÄSLE Abstract A long-term pump test was conducted in the KTB pilot borehole (KTB-VB), located in the Oberpfalz area, Germany. It produced 22 300 m3 of formation fluid. Initially, fluid production rate was 29 l min,1 for 4 months, but was then raised to an average of 57 l min,1 for eight more months. The aim of this study was to examine the fluid parameters and hydraulic properties of fractured, crystalline crusts as part of the new KTB programme ,Energy and Fluid Transport in Continental Fault Systems'. KTB-VB has an open-hole section from 3850 to 4000 m depth that is in hydraulic contact with a prominent continental fault system in the area, called SE2. Salinity and temperature of the fluid inside the borehole, and consequently hydrostatic pressure, changed significantly throughout the test. Influence of these quantities on variations in fluid density had to be taken into account for interpretation of the pump test. Modelling of the pressure response related to the pumping was achieved assuming the validity of linear Darcy flow and permeability to be independent of the flow rate. Following the principle ,minimum in model dimension', we first examined whether the pressure response can be explained by an equivalent model where rock properties around the borehole are axially symmetric. Calculations show that the observed pressure data in KTB-VB can in fact be reproduced through such a configuration. For the period of high pumping rate (57 l min,1) and the following recovery phase, the resulting parameters are 2.4 × 10,13 m3 in hydraulic transmissivity and 3.7 × 10,9 m Pa,1 in storativity for radial distances up to 187 m, and 4.7 × 10,14 m3 and 6.0 × 10,9 m Pa,1, respectively, for radial distances between 187 and 1200 m. The former pair of values mainly reflect the hydraulic properties of the fault zone SE2. For a more realistic hydraulic study on a greater scale, program FEFLOW was used. Parameter values were obtained by matching the calculated induced pressure signal to fluid-level variations observed in the KTB main hole (KTB-HB) located at 200 m radial distance from KTB-VB. KTB-HB is uncased from 9031 to 9100 m and shows indications of leakage in the casing at depths 5200,5600 m. Analysis of the pressure record and hydraulic modelling suggest the existence of a weak hydraulic communication between the two boreholes, probably at depths around the leakage. Hydraulic modelling of a major slug-test in KTB-HB that was run during the pumping in KTB-VB reveals the effective transmissivity of the connected formation to be 1 to 2 orders of magnitude lower than the one determined for the SE2 fault zone. [source] Estimating monthly surface winds for Scania, southern Sweden, using geostrophic wind (1899,1997)GEOGRAFISKA ANNALER SERIES A: PHYSICAL GEOGRAPHY, Issue 2 2002Marie Ekström Wind direction conditions during the 20th century in Scania, southern Sweden, are investigated using an estimated series of monthly wind vector components (east,west u component and north,south v component). The series is developed from a regression relationship between pairwise (1973 to 1997) monthly averages of 10,m surface wind from Scania and a monthly geostrophic wind, based on mean sea level (MSL) pressure data from the National Center of Atmospheric Research (NCAR). The wind conditions during the 20th century are dominated by winds from southwesterly and westerly directions, particularly during summer and autumn. From the 1980s onwards, increased frequencies of westerly winds are evident in spring and summer; however, similarly large frequencies of westerly winds are also found during the early part of the 20th century. Analysis of the estimated wind series indicates large variation in wind direction during the investigated time period, particularly during 1930 to 1960 when large increases of easterly winds are evident in spring. Increased frequencies of easterly winds were also found in other months during this period but not to the same extent as during the spring season. Thus, the presence of periods with quite different wind characteristics suggests that the overall atmospheric circulation has experienced some shifts in this region during the 20th century. [source] European snow cover extent variability and associations with atmospheric forcingsINTERNATIONAL JOURNAL OF CLIMATOLOGY, Issue 10 2010Gina R. Henderson Abstract Snow cover in Europe represents an important component of the region's climatic system. Variability in snow cover extent can have major implications on factors such as low-level atmospheric temperatures, soil temperatures, soil moisture, stream discharge, and energy allocation involved in the warming and melting of the snowpack. The majority of studies investigating Northern Hemisphere snow cover identify European snow cover extent as a portion of the Eurasian record, possibly masking complexities of this subset. This study explores the variability of European snow cover extent from 1967,2007, with the region in question including the area of Europe extending eastward to the Ural Mountains (60°E). Using the 89 × 89 gridded National Oceanic and Atmospheric Administration (NOAA) Northern Hemisphere weekly satellite snow cover product, area estimates of seasonal snow cover were calculated, and their relationship to gridded temperature, precipitation, and sea-level pressure data analysed. The spatial variability of snow cover extent was also explored using geographical information systems (GIS). The combined results from both surface temperature and precipitation analyses point towards snow cover extent in Europe being primarily temperature dependent. Atmospheric variables associated with extremes in snow cover extent were investigated. Large (small) European snow extent is associated with negative (positive) 850 hPa zonal wind anomalies, negative (positive) European 1000,500 hPa thickness anomalies, and generally positive (negative) Northern European precipitation anomalies. Sea-level pressure and 500 hPa results indicate strong associations between large (small) snow cover seasons and the negative (positive) phase of the North Atlantic Oscillation. Copyright © 2009 Royal Meteorological Society [source] The latitude of the subtropical ridge over Eastern Australia: The L index revisitedINTERNATIONAL JOURNAL OF CLIMATOLOGY, Issue 10 2005Wasyl Drosdowsky Abstract Recent research has suggested that the position of the subtropical ridge in mean sea-level pressure over eastern Australia, referred to as the L index, has undergone a substantial poleward shift over the past century. These findings are not supported by calculations of the L index based on daily National Centers for Environmental Prediction reanalysis from 1948 to 2002, and on monthly mean Australian pressure data from 1890 to 2003. Reasons for these differences are discussed, together with the relationship between the L index and Australian rainfall. Copyright © 2005 Royal Meteorological Society [source] Towards ice-core-based synoptic reconstructions of west antarctic climate with artificial neural networksINTERNATIONAL JOURNAL OF CLIMATOLOGY, Issue 5 2005David B. Reusch Abstract Ice cores have, in recent decades, produced a wealth of palaeoclimatic insights over widely ranging temporal and spatial scales. Nonetheless, interpretation of ice-core-based climate proxies is still problematic due to a variety of issues unrelated to the quality of the ice-core data. Instead, many of these problems are related to our poor understanding of key transfer functions that link the atmosphere to the ice. This study uses two tools from the field of artificial neural networks (ANNs) to investigate the relationship between the atmosphere and surface records of climate in West Antarctica. The first, self-organizing maps (SOMs), provides an unsupervised classification of variables from the mid-troposphere (700 hPa temperature, geopotential height and specific humidity) into groups of similar synoptic patterns. An SOM-based climatology at annual resolution (to match ice-core data) has been developed for the period 1979,93 based on the European Centre for Medium-Range Weather Forecasts (ECMWF) 15-year reanalysis (ERA-15) dataset. This analysis produced a robust mapping of years to annual-average synoptic conditions as generalized atmospheric patterns or states. Feed-forward ANNs, our second ANN-based tool, were then used to upscale from surface data to the SOM-based classifications, thereby relating the surface sampling of the atmosphere to the large-scale circulation of the mid-troposphere. Two recorders of surface climate were used in this step: automatic weather stations (AWSs) and ice cores. Six AWS sites provided 15 years of near-surface temperature and pressure data. Four ice-core sites provided 40 years of annual accumulation and major ion chemistry. Although the ANN training methodology was properly designed and followed standard principles, limited training data and noise in the ice-core data reduced the effectiveness of the upscaling predictions. Despite these shortcomings, which might be expected to preclude successful analyses, we find that the combined techniques do allow ice-core reconstruction of annual-average synoptic conditions with some skill. We thus consider the ANN-based approach to upscaling to be a useful tool, but one that would benefit from additional training data. Copyright © 2005 Royal Meteorological Society. [source] The annual cycle and interannual variability of atmospheric pressure in the vicinity of the North PoleINTERNATIONAL JOURNAL OF CLIMATOLOGY, Issue 10 2003Richard I. Cullather Abstract A comparison of National Centers for Environmental Prediction,National Center for Atmospheric Research reanalysis six-hourly sea-level pressure data with former Soviet drifting station observations over the central Arctic Basin reveals high monthly correlations throughout the period 1950,91, but also a preferred winter season negative bias of about 1.4 hPa. Using the reanalysis, supplemented by Arctic Ocean Buoy Program fields and in situ observations, a generalized depiction of the annual cycle of pressure fields over the Arctic may be constructed. Above the Canada Basin,Laptev Sea side of the Arctic, the annual cycle of surface pressure is dominated by the first harmonic, which has an amplitude of about 5 hPa and maximum pressure occurring in March. Along the periphery of northern Greenland and extending to the North Pole, a weak semiannual cycle is found in surface pressure with maxima in May and November. The presence of the semiannual variation over time is highly variable. Dynamically, this progression of the annual cycle may be attributed to the transfer of atmospheric mass from Eurasia and into the Canadian Archipelago in spring and the reverse condition in autumn. Over the central Arctic Basin, springtime pressure increases result from an enhanced poleward mass transport from Eurasia. An increase of equatorward transport over the Canadian Archipelago in May and June results in central Arctic pressure decreases into summer. A less distinct temporal separation between the poleward Canadian transport and the equatorward Eurasian transport results in the weaker second pressure maximum in autumn. On interannual time-scales, atmospheric mass over the central Arctic is exchanged with the storm track centres of action in the North Atlantic and North Pacific. In particular, the large decrease in central Arctic Basin sea-level pressure during the late 1980s is due to a large transfer of atmospheric mass into the North Pacific. Copyright © 2003 Royal Meteorological Society [source] Odontocete suction feeding: Experimental analysis of water flow and head shapeJOURNAL OF MORPHOLOGY, Issue 12 2006Alexander J. WerthArticle first published online: 13 NOV 200 Abstract The role of cranial morphology in the generation of intraoral and oropharyngeal suction pressures in odontocetes was investigated by manipulating the jaw and hyolingual apparatus of submerged heads of three species presenting varied shapes. Hyoid and gular muscles were manually employed to depress and retract the tongue. Pressures were recorded at three locations in the oral cavity, as gape and site, speed, and force of pull were varied. A biomechanical model was also developed to evaluate pressure data. The species with the shortest, bluntest head and smallest mouth opening generated greater negative pressures. Suction generation diminished sharply as gape increased. Greatest negative pressures attained were around ,45 mmHg (,6,000 Pa), a magnitude deemed suitable for capture of small live prey. Odontocetes utilizing this bidirectional flow system should profit by evolution of a rounder mouth opening through progressive shortening and widening of the rostrum and jaws, a trend evident in cranial measurements from fossil and recent odontocetes. Blunt heads correlate with anatomical, ecological, and behavioral traits associated with suction feeding. Small-gape suction (with minimally opened jaws) could be used by odontocetes of all head and oral shapes to draw prey sufficiently close to the mouth for suction ingestion or grasping via dentition. Principal limitations of the experimental and mathematical simulations include assumption of a stationary odontocete with static (open or closed) jaws and potential scaling issues with differently sized heads and gapes. J. Morphol., 2006. © 2006 Wiley-Liss, Inc. [source] MAPPING AND CLASSIFYING FLOW UNITS IN THE UPPER PART OF THE MID-CRETACEOUS SARVAK FORMATION (WESTERN DEZFUL EMBAYMENT, SW IRAN) BASED ON A DETEMINATION OF RESERVOIR ROCK TYPESJOURNAL OF PETROLEUM GEOLOGY, Issue 4 2007B. Beiranvand The mid-Cretaceous Sarvak Formation, the second-most important reservoir unit in Iran, is composed mainly of grain-supported carbonates. For the purposes of this study, flow units in the upper part of the formation were identified, mapped and classified as part of an integrated reservoir characterization study at a giant oilfield in SW Iran. Pore types and geometries, pore-scale diagenetic history and core-scale depositional attributes were logged using conventional petrographic and lithological methods. The resulting data were combined with core descriptions, mercury-injection capillary pressure data, and wireline log and geophysical data to identify five reservoir rock types: (i) highly oil-stained, grain-supported carbonates, including patch reef and barrier complex deposits with high porosities and permeabilities; (ii) leeward and seaward shoal deposits including grain-supported packstones and skeletal wackestones with high porosities and permeabilities; (iii) dominantly mud-supported lagoonal and open-marine facies with fair porosity and permeability; (iv) grain-supported but highly cemented facies which had poor reservoir characteristics; and (v) calcareous shales and shaly limestones with no reservoir quality. Based on the reservoir rock types, eight flow units were recognised. Subsequently, four reservoir zones were defined based on these flow units at a field scale. This study has contributed to our understanding of flow units in this complex carbonate reservoir, and has improved our ability to characterize and model the architecture of the reservoir from pore to core to field scale. [source] GEOLOGICAL MODEL EVALUATION THROUGH WELL TEST SIMULATION: A CASE STUDY FROM THE WYTCH FARM OILFIELD, SOUTHERN ENGLANDJOURNAL OF PETROLEUM GEOLOGY, Issue 1 2007S.Y. Zheng This paper presents an approach to the evaluation of reservoir models using transient pressure data. Braided fluvial sandstones exposed in cliffs in SW England were studied as the surface equivalent of the Triassic Sherwood Sandstone, a reservoir unit at the nearby Wytch Farm oilfield. Three reservoir models were built; each used a different modelling approach ranging in complexity from stochastic pixel-based modelling using commercially available software, to a spreadsheet random number generator. In order to test these models, numerical well test simulations were conducted using sector models extracted from the geological models constructed. The simulation results were then evaluated against the actual well test data in order to find the model which best represented the field geology. Two wells at Wytch Farm field were studied. The results suggested that for one of the sampled wells, the model built using the spreadsheet random number generator gave the best match to the well test data. In the well, the permeability from the test interpretation matched the geometric average permeability. This average is the "correct" upscaled permeability for a random system, and this was consistent with the random nature of the geological model. For the second well investigated, a more complex "channel object" model appeared to fit the dynamic data better. All the models were built with stationary properties. However, the well test data suggested that some parts of the field have different statistical properties and hence show non-stationarity. These differences would have to be built into the model representing the local geology. This study presents a workflow that is not yet considered standard in the oil industry, and the use of dynamic data to evaluate geological models requires further development. The study highlights the fact that the comparison or matching of results from reservoir models and well-test analyses is not always straightforward in that different models may match different wells. The study emphasises the need for integrated analyses of geological and engineering data. The methods and procedures presented are intended to form a feedback loop which can be used to evaluate the representivity of a geological model. [source] GEOLOGICAL INTERPRETATION OF WELL TEST ANALYSIS: A CASE STUDY FROM A FLUVIAL RESERVOIR IN THE GULF OF THAILANDJOURNAL OF PETROLEUM GEOLOGY, Issue 1 2003S. Y. Zheng One problem with the inversion of transient well test data is that it can yield a non-unique solution. The uncertainty resulting from this type of approach can only be resolved by considering information from another source such as geology. Geological information will help to define the interpretation model which will ensure the correct analysis of the well test data. The results of well test analyses are of little value to reservoir characterisation and modelling unless they can be explained from a geological point of view. This last step is what we refer to here as geological interpretation. Other sources of information which can help with well test analyses come from seismic surveys and petrophysics. Modern well test interpretation therefore consists of two major steps: analysis of the well test data; and interpretation of the results. In detail, this should include the following: 1definition of an interpretation model , this requires the integration of geological, seismic and petrophysical data with transient pressure data 2analysis of the well test data based on the interpretation model defined 3geological interpretation of the results, which is necessary in order to explain or give meaning to the results. In this paper, we present a case study from a fluvial gas reservoir in the Gulf of Thailand which demonstrates these procedures. In the context of a defined geological environment, a transient pressure test has been fully analysed. Newly-developed software based on the finite element method has been used to forward model the test scenarios. This allowed the results of seismic and petrophysical analyses to be integrated into the well test model. This case study illustrates the integrated use of geological, petrophysical, well test and seismic attribute data in defining a reservoir model which respects both the reservoir geometry at some distance from the well location and also the reservoir's heterogeneity. We focus on a particular well in the Pattani Basin at which conventional well test analyses have been conducted. By considering the results of these analyses, forward modelling was carried out in which the drainage area was "cut" out of the structural map defined by seismic interpretation; also, the formation's internal heterogeneity was modelled according to well logs and petrophysical analyses. Finally, analytical and simulation results were compared with the transient pressure data. We conclude that the integration of geological, seismic, petrophysical and well test data greatly reduced uncertainties in well test interpretation. The consistency of the results and the fact that they satisfied all the relevant disciplines meant that much more confidence could be given to their interpretation. [source] Thermal Decomposition of NTO: An Explanation of the High Activation EnergyPROPELLANTS, EXPLOSIVES, PYROTECHNICS, Issue 4 2007Valery Abstract Burning rate characteristics of the low-sensitivity explosive 5-nitro-1,2,4-triazol-3-one (NTO) have been investigated in the pressure interval of 0.1,40,MPa. The temperature distribution in the combustion wave of NTO has been measured at pressures of 0.4,2.1,MPa. Based on burning rate and thermocouple measurements, rate constants of NTO decomposition in the molten layer at 370,425,°C have been derived from a condensed-phase combustion model (k=8.08,1013,exp(,19420/T) s,1. NTO vapor pressure above the liquid (ln P=,9914.4/T+14.82) and solid phases (ln P=,12984.4/T+20.48) has been calculated. Decomposition rates of NTO at low temperatures have been defined more exactly and it has been shown that in the interval of 180,230,°C the decomposition of solid NTO is described by the following expression: k=2.9,1012,exp(,20680/T). Taking into account the vapor pressure data obtained, the decomposition of NTO in the gas phase at 240,250,°C has been studied. Decomposition rate constants in the gaseous phase have been found to be comparable with rate constants in the solid state. Therefore, a partial decomposition in the gas cannot substantially increase the total rate. High values of the activation energy for solid-state decomposition of NTO are not likely to be connected with a sub-melting effect, because decomposition occurs at temperatures well below the melting point. It has been suggested that the abnormally high activation energy in the interval of 230,270,°C is a consequence of peculiarities of the NTO transitional process rather than strong bonds in the molecule. In this area, the NTO molecule undergoes isomerization into the aci -form, followed by C3-N2 heterocyclic bond rupture. Both processes depend on temperature, resulting in an abnormally high value of the observed activation energy. [source] Functional analysis of the gibbon foot during terrestrial bipedal walking: Plantar pressure distributions and three-dimensional ground reaction forcesAMERICAN JOURNAL OF PHYSICAL ANTHROPOLOGY, Issue 3 2005Evie Vereecke Abstract This paper gives a detailed analysis of bipedal walking in the white-handed gibbon, based on collected pressure and force data. These data were obtained from four gibbons in the Wild Animal Park, Planckendael, Belgium, by using a walkway with integrated force plate and pressure mat. This is the first study that collects and describes dynamic plantar pressure data of bipedally walking gibbons, and combines these with force plate data. The combination of these data with previously described roll-off patterns of gibbons, based on general observations, video images, force plates, and EMG data, gives us a detailed description of foot function during gibbon bipedalism. In addition, we compare the observed characteristics of hylobatid bipedalism with the main characteristics of bonobo and human bipedalism. We found that gibbons are midfoot/heel plantigrade, and lack the typical heel-strike of other hominoids. The hallux is widely abducted and touches down at the onset of the stance phase, which results in an L-shaped course of the center of pressure. The vertical force curve is trapezoid to triangular in shape, with high peak values compared to humans. The braking component is shorter than the accelerating component, and shortens further at higher walking velocities. Speed has a significant influence on the forefoot peak pressures and on most of the defined gait parameters (e.g., vertical force peak), and it alters the foot contact pattern as well. The investigation of existing form-function relationships in nonhuman primates is essential for the interpretation of fossil remains, and might help us understand the evolution of habitual bipedal walking in hominids. Am J Phys Anthropol, 2005. © 2005 Wiley-Liss, Inc. [source] Triggering of systolic arterial pressure alarms using statistics-based versus threshold alarms,ANAESTHESIA, Issue 2 2009C. W. Connor Summary Threshold systolic arterial pressure alarms often use pre-operative values as a guide for intra-operative values. Recently, two systems (normalisation and principal component analysis) have been described that use the ,current' systolic arterial pressure and the change in systolic arterial pressure over a preceding time interval to generate an alarm based on units of standard deviation. Normalisation and principal component analysis techniques should prioritise alarms for clinically significant changes and hence reduce overall activation of alarms. Our aim was to measure the change in alarm activation using these techniques compared with standard threshold alarms. Systolic blood pressure data, collected from 10 patients (a total of 2177 min at 100 Hz), were cleaned and submitted to analysis using threshold alarms, normalisation and principal component analysis. With the threshold alarms set at 100 mmHg (low) and 140 mmHg (high), and a 5-min window, the alarms were activated for 557 min; using statistics-based thresholds the alarms were activated for 169 min (normalisation) and 155 min (principal component analysis), a reduction of approximately 70,72%. [source] Assessment of third degree tears using three-dimensional anal endosonography with combined anal manometry: a novel techniqueBJOG : AN INTERNATIONAL JOURNAL OF OBSTETRICS & GYNAECOLOGY, Issue 7 2002A.B. Williams Three-dimensional anal endosonography has enabled sagittal and coronal reconstructions of the anal canal to be matched with longitudinal pressure data, to present a combined picture of structure and function. This novel technique has been applied to a group of women with a clinical diagnosis of a third degree tear. Endosonography showed that only 68% of women had ultrasound evidence of sphincter damage. Anal canal anatomy and pressure profile did not differ significantly between those with and those without sphincter damage, but the anterior external anal sphincter and the puborectalis tended to be shorter and the pressures were lower in those with sphincter disruption. [source] On the Analyses of Mixture Vapor Pressure Data: The Hydrogen Peroxide/Water System and Its Excess Thermodynamic FunctionsCHEMISTRY - A EUROPEAN JOURNAL, Issue 24 2004Stanley L. Manatt Dr. Abstract Reported here are some aspects of the analysis of mixture vapor pressure data using the model-free Redlich,Kister approach that have heretofore not been recognized. These are that the pure vapor pressure of one or more components and the average temperature of the complex apparatuses used in such studies can be obtained from the mixture vapor pressures. The findings reported here raise questions regarding current and past approaches for analyses of mixture vapor pressure data. As a test case for this analysis approach the H2O2,H2O mixture vapor pressure measurements reported by Scatchard, Kavanagh, and Tickner (G. Scatchard, G. M. Kavanagh, L. B. Ticknor, J. Am. Chem. Soc.1952, 74, 3715,3720; G. M. Kavanagh, PhD. Thesis, Massachusetts Institute of Technology (USA), 1949) have been used; there is significant recent interest in this system. It was found that the original data is fit far better with a four-parameter Redlich,Kister excess energy expansion with inclusion of the pure hydrogen peroxide vapor pressure and the temperature as parameters. Comparisons of the present results with the previous analyses of this suite of data exhibit significant deviations. A precedent for consideration of iteration of temperature exists from the little-known work of Uchida, Ogawa, and Yamaguchi (S. Uchida, S. Ogawa, M. Yamaguchi, Japan Sci. Eng. Sci.1950, 1, 41,49) who observed significant variations of temperature from place to place within a carefully insulated apparatus of the type traditionally used in mixture vapor pressure measurements. For hydrogen peroxide, new critical constants and vapor pressure,temperature equations needed in the analysis approach described above have been derived. Also temperature functions for the four Redlich,Kister parameters were derived, that allowed calculations of the excess Gibbs energy, excess entropy, and excess enthalpy whose values at various temperatures indicate the complexity of H2O2,H2O mixtures not evident in the original analyses of this suite of experimental results. [source] | |||||||||||||||||||